Triazine ring substituted phenylsulfonyl urea compound, preparation method therefor, herbicidal composition and use

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a triazine ring substituted phenylsulfonyl urea compound, a preparation method therefor, a herbicidal composition and a use. The compound is as shown in general formula I, wherein Z is hydrogen or alkyl; R is alkyl, haloalkyl or alkoxy. The compound has excellent herbicidal activity on gramineous weeds, broadleaf weeds etc.

Description

A triazine ring substituted phenylsulfonylurea compound, preparation method thereof, herbicide composition and application thereof Technical Field

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

[0002] Weed control is a crucial step in achieving efficient agriculture. Despite the diverse range of herbicides available on the market, such as patent WO2012059050A1, which discloses the use of substituted biarylbenzenesulfonamides as herbicides, these known compounds, however, offer less than satisfactory herbicidal performance against harmful plants and crop selectivity. Furthermore, the expanding market, weed resistance, drug shelf life, and affordability, coupled with growing environmental awareness, necessitate continuous research and development of new, highly effective, safe, and economical herbicides with diverse modes of action.

[0003] Summary of the Invention

[0004] The present invention provides a triazine ring-substituted phenylsulfonylurea compound, a preparation method thereof, a herbicidal composition and an 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.

[0005] The technical solution adopted in the present invention is as follows:

[0006] A triazine ring-substituted phenylsulfonylurea compound, as shown in general formula I:

[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 definitions 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 terms, represent the following substituents: Alkyl groups having more than two carbon atoms may 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; and 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 general formula II is reacted with the compound represented by general formula III to obtain the compound represented by general formula I. The chemical reaction equation is as follows:

[0018] 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.

[0019] In one embodiment, the reaction is carried out in the presence of a base and a solvent.

[0020] 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)].

[0021] In another 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.

[0022] The compounds of the present invention can also be prepared by referring to the methods described in WO2012059050A1, WO2006114220A1, US06 / 396959 or US06 / 458799.

[0023] 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.

[0024] 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.

[0025] 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 compound is used to control weeds in useful crops, which are transgenic crops or crops treated with genome editing technology.

[0026] 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 that 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 mentioned in particular, without being limited to specific species. Examples of weed species on which the active substances are effective include monocotyledonous plants: annual Avena, Secale, Grass, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria, and Cyperus, and perennial Agropyron, Cyperus, Imperata, and Sorghum, as well as perennial Cyperus.

[0027] Regarding dicotyledonous weed species, its activity can be extended to species such as annual Galium, Viola, Veronica, Sesame, Chickweed, Amaranthus, Sinapsis, Ipomoea, Glechoma, Matricaria, and Abutilon, as well as perennial weeds such as Convolvulus, Thistle, Rumex, and Artemisia. The active ingredients of the present invention effectively control harmful plants such as Echinochloa, Sagittaria, Alisma, Eriocheir, Saccharum, and Cyperus under unspecified conditions during rice sowing. If applied to the soil surface before germination, the weed seedlings can be completely prevented from emerging, or growth can be halted as soon as the cotyledons emerge, ultimately resulting in complete death after three to four weeks. The compounds of the present invention are particularly active against Apia, Sesame, Polygonum convolvulus, Chickweed, Ivy-leaved Veronica, Veronica arabicum, Pansy, Amaranthus, Galium, and Kochia.

[0028] While the compounds of the present invention exhibit excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they cause no damage, or only minimal damage, to economically important crop plants such as wheat, barley, rye, rice, corn, sugar beets, cotton, and soybeans. They are particularly compatible with cereal crops such as wheat, barley, and corn, particularly wheat. Therefore, the compounds of the present invention are well suited for selectively controlling undesirable plants in agricultural or ornamental crops.

[0029] 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 often possess superior properties, such as resistance to specific pesticides, especially herbicides, or resistance to plant diseases or their causative microorganisms, such as specific insects or fungal, bacterial, or viral microorganisms. Other specific properties are related to the product's characteristics, such as quantity, quality, storage stability, composition, and specific ingredients. Thus, transgenic plant products are known to be obtained with increased starch content, improved starch quality, or a different fatty acid composition.

[0030] The compounds of formula I according to the present invention or their salts are preferably used in the cultivation of economically important genetically modified crops and ornamental plants, for example cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn, or in the cultivation of sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants. The compounds of formula I are preferably used in the cultivation of useful plants with herbicides which are resistant or have been rendered resistant to the toxic effects of the herbicides by genetic engineering.

[0031] Conventional methods for breeding plants with improved traits 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-0221044 A, EP-0131624 A). For example, several methods have been described:

[0032] - genetic engineering of crop plants to improve starch synthesis in plants (e.g. WO 92 / 11376, WO 92 / 14827, WO 91 / 19806);

[0033] - transgenic crop plants resistant to specific herbicides, such as glufosinate herbicides (e.g. EP-0242236 A, EP-0242246 A) or glyphosate herbicides (WO 92 / 00377), or sulfonylurea herbicides (EP-0257993 A, US Pat. No. 5,013,659 A);

[0034] - genetically modified crop plants, such as cotton, that produce Bacillus thuringiensis toxins (Bt toxins) that protect against attack by certain pests (EP-0142924 A, EP-0193259 A);

[0035] - Transgenic crop plants with improved fatty acid composition (WO 91 / 13972).

[0036] Numerous molecular biotechniques are known for producing transgenic plants with improved traits (see, for example, Sambrook et al., 1989, Molecular Amplification, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, New York; or Winnacker, "Gene und Klone," VCH Weinheim, 2nd ed., 1996, or Christou, "Trends in Plant Science," 1 (1996), 423-431). To carry out genetic engineering operations, nucleic acid molecules can be introduced into plasmids, and mutations or sequence changes can be generated by recombination of DNA sequences. Using the standard methods described above, for example, substrates can be exchanged, partial sequences can be removed, or natural or synthetic sequences can be added. To connect DNA fragments to one another, it is possible to attach binding partners or linkers to the fragments.

[0037] Plant cells in which the activity of a gene product is reduced can be prepared, for example, by expressing at least one appropriate antisense RNA, sense RNA to achieve a cosuppression effect, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of the gene product.

[0038] For this purpose, it is possible to use a DNA molecule that comprises the entire coding sequence of the gene product, including any flanking sequences that may be present, and to use a DNA molecule that comprises only a portion of the coding sequence, which portion must be long enough to achieve an antisense effect in the cell. Sequences that are highly homologous to the coding sequence of the gene product, but not identical thereto, can also be used.

[0039] When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, in order to localize in a specific compartment, it is possible, for example, to link the coding region to 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).

[0040] Transgenic plant cells can be incorporated into whole plants using known techniques. Transgenic plants can be of any desired plant variety, i.e., monocotyledons and dicotyledons. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (=natural) genes or gene sequences, or by expressing heterologous (=foreign) genes or gene sequences.

[0041] When the active substances of the present invention are used on genetically modified crops, in addition to the harmful plant growth inhibitory effects observed on other crops, they often exhibit specific effects on the corresponding genetically modified crops, such as improved or expanded weed control, improved application rates, preferably a good combination of the resistance of the genetically modified crop and the performance of the herbicide, and effects on the growth and yield of the genetically modified crop plants. Therefore, the present invention also provides the use of the compounds as herbicides for controlling harmful plants in genetically modified crop plants.

[0042] Furthermore, the compounds of the present invention can significantly regulate the growth of crop plants. By modulating plant metabolism, these compounds can be used to control plant composition and promote harvest, for example by causing plant desiccation and dwarfing. Furthermore, they are suitable for regulating and inhibiting undesirable plant growth without disrupting crop growth. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops because it can reduce or completely prevent lodging.

[0043] The compound 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 common 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, emulsion concentrates (EC), emulsions 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), seeded 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], Vol. 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.

[0044] Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives are likewise known and described in, for example, Watkins, "Handbook of Powder Diluents, Pesticides and Carriers," 2nd ed., Darland, Caldwell, NJ; Hvophen, "Introduction to Clay Colloid Chemistry," 2nd ed., J. Wiley and Sons, NY; C. Marsden, "Solvent Guide," 2nd ed., 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], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986.

[0045] Wettable powders are homogeneously dispersible in water and contain, in addition to the active substance, a diluent or inert substance, 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 herbicide active substance is finely ground, for example using conventional apparatus such as hammer mills, fan mills or jet mills, and the adjuvants are mixed in simultaneously or sequentially.

[0046] The concentrated emulsion is prepared by dissolving the active substance in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of relatively high-boiling aromatic compounds or hydrocarbons or solvents, and adding one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers that can be used are calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl 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 acid esters.

[0047] 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 in 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 the type described above for the other formulations.

[0048] 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 desired, adding surfactants of another formulation type as described above.

[0049] Granules can be prepared by spraying the active substance onto an adsorbent and granulating with an inert material, or by concentrating the active substance onto 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 using methods for preparing fertilizer granules and, if desired, mixed with fertilizers. Aqueous suspension granules can be prepared using conventional methods, such as spray drying, fluidized bed granulation, disc granulation, mixing using a high-speed mixer, and extrusion in the absence of solid inert materials.

[0050] For the preparation of granules using a mill, fluidized bed, extruder, and spraying, see, for example, the following processes: "Spray Drying Handbook," 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration," Chemistry and Engineering, 1967, pp. 147ff; "Perry's Chemical Engineer's Handbook," 5th ed., McGraw-Hill, New York, 1973, pp. 8-57. For the formulation of crop protection products, see, for example, G. C. Lingman, "Weed Control as a Science," John Wiley & Sons, New York, 1961, pp. 81-96 and J. D. Frieder, S. A. Evans, "Weed Control Handbook," 5th ed., Blackwell Scientific Research, Oxford, 1968, pp. 101-103.

[0051] Agrochemical formulations typically contain 0.1 to 99% by weight, particularly 0.1 to 95% by weight, of the active substance of Formula I. The active substance concentration in wettable powders is, for example, from about 10 to 99% by weight, with the formulation components typically comprising the remainder to 100% by weight. The active substance concentration in emulsifiable concentrates can range from about 1 to 90% by weight, preferably 5 to 80%. Powder formulations contain 1 to 30% by weight of active substance, typically preferably 5 to 20% by weight, while sprayable solutions contain approximately 0.05 to 80% by weight, preferably 2 to 50% by weight. The active substance content in water-suspendable granules depends primarily on whether the active substance is liquid or solid, and on the adjuvants, fillers, etc. used in granulation. The active substance content in water-suspendable granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

[0052] The active substance formulations may additionally include tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and, generally, pH and viscosity regulators which are customary in each case.

[0053] Based on these formulations, it is also possible to mix with other pesticide active substances such as insecticides, acaricides, herbicides and fungicides, as well as with safeners, fertilizers and / or plant growth regulators, either as premixes or as canned mixes.

[0054] In mixed formulations or tank-mixed formulations, suitable active substances that can be mixed with the active substance of the present invention are, for example, known substances described in "World New Pesticide Variety Technology Encyclopedia", China Agricultural Science and Technology Press, September 2010, 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, isopropyl metolachlor, isopropyl metolachlor, S-isopropyl metolachlor, pretilachlor, acetochlor, acetochlor, naphthiachlor, R-(l-)naphthiachlor, propanil, mefenacet, bisbencarb, fluazifop, flufenacet, cyfluthrin, flumethalin, bromomethalin, dimethathiachlor, high-efficiency dimethathiachlor, ethoxymethalin, flufenacet, methoxymethalin, metazachlor, isopropyltrimonium chloride, high-efficiency cyfluthrin, Dipropylene glycol, pethoxachlor, butyrac, cyproconazole, flumethalin, heptamiprole, isobutachlor, propargyl chloramine, terbutachlor, dimethylaminopropylamine, dimethoate, chlorfenapyr, trimethylcyclohexane, chlorfenapyr, propyracyl chloramine, valeryl chloramine, carbamyl, new Yanling, tricyclic chlorfenapyr, butenesulfonamide, butenesulfonamide, mesotrione, benzylchlor, quinone, benzfluorosulfonamide, naphthamide, acetoacetamide, naphthamide, thiazolin, cypermethrin, benzylchlor, benzylchlor, cypermethrin, benzylchlor, cypermethrin, atrazine, simazine, promethazine, cyanamide, simethazine, ametryn, propazine, isopropylamine, fluroxypyr, terbutylamine, terbutylazine, triazine fluazifone, cyprodinil, gampopazine, thiophanate , Promethazine, Simatolin, Azide, Dichlorvos, Isopropylamine, Cyprodinil, Metazine, Another Butylazine, Second Butylazine, Terbutalone, Methoxypropylamine, Cyanamide, Cyanocyanine, Kolazone, Atrazine, Metazine, Glycyrrhizin, Cyanuric acid, Indaziflam, Chlorsulfuron, Metsulfuron-methyl, Bensulfuron-methyl, Chlorimuron-methyl, Bensulfuron-methyl, Thisulfuron-methyl, Pyrazosulfuron-methyl, Metsulfuron-methyl, Iodosulfuron-methyl sodium salt, Formamidosulfuron-methyl, Ethylsulfuron-methyl, Bensulfuron-methyl, Metsulfuron-methyl, Nicosulfuron, Ethamidosulfuron-methyl, Acesulfuron-methyl, Ethoxysulfuron-methyl, Cyprodinil, Sulfonsulfuron-methyl, Tetrazosulfuron, Fentazuron-methyl, Monosulfuron-methyl, Monosulfuron, Fluazuron-methyl, Flupyrazosulfuron-methyl, Epoxysulfuron Sulfur-methyl, azole pyrazosulfuron, primisulfuron, propensulfuron-methyl, trifloxysulfuron, sulfosulfuron, trifloxysulfuron, trifloxysulfuron, metsulfuron-methyl sodium, primisulfuron, methylthiosulfuron, pyrimidisulfon-methyl, Propyrisulfuron (propyrisulfuron), pyrazosulfuron-methyl, acifluorfen, fomesafen, lactofen, fluazifop-butyl, oxyfluorfen, oxazolidinone, benfibrate, chlorpyrifos ethyl, methylcarboxylic acid butyl, trifluoroacetic acid butyl, methoxy-nitropropane, trifluosuccinate, fluorinated herbicide ether, flutosulfuron, nitropropane, methylpyralid, dimethoate, flutosulfuron, flutosulfuron ester, Halosafen, chlorotoluron, isoproturon, linuron, diuron,Saproron, fluuron, benzylthiocarb, methyl benzylthiocarb, benzylthiocarb, sulfothiocarb, isoxalon, terbuthiuron, clodinafuron, chlorbrom, methylthiocarb, acetylthiocarb, methoxythiocarb, bromothiocarb, methoxythiocarb, greenthiocarb, cyclomethuron, fenothuron, flusulfuron, chlorthiocarb ... Methiuron, Chloreturon, Tetrafluoroethylene, Betaine, Betaine-ethyl ester, Betaine, Sulfur, Tetrasodium, Avenaline, Afenacet, Chlorpropamine, Dichlorobenzyl, Methiol, Chlorpropamine, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butylcarb, Methiol, Methiol, Wild wheat dapoxetine, Piperidin, Methiol, Echinopsin, Cyclohexanil, Avenaline, Junda, Ethiocarb, Pingcaodan, Kecaodan, Benthiocarb, Zhongcaodan, Sulfadimethoxam, Methiol, Is opolinate, Methiobencarb, 2,4-D butyl ester, 2-methyl-4-chloro sodium, 2,4-D isooctyl ester, 2-methyl-4-chloroisooctyl ester, 2,4-D sodium salt, 2,4-D dimethylamine salt, 2-methyl-4-chloroethyl thioester, 2-methyl-4-chloro, 2,4-D propionic acid, high 2,4-D propionic acid salt, 2,4-D butyric acid, 2-methyl-4-chloropropionic acid, 2-methyl-4-chloropropionic acid salt, 2-methyl-4-chlorobutyric acid, 2,4,5-T, 2,4,5-T propionic acid, 2,4,5-T butyric acid, 2-methyl-4-chloramine salt, dicamba, cypermethrin, cypermethrin, trichlorobenzoic acid, ammonia dichlorobenzoic acid, methoxytrichlorobenzoic acid, diclofenac, pyrimethoxybenzoic acid Cyclohexanil, fluazifop-butyl, fluazifop-butyl, high-efficiency fluazifop-butyl, quizalofop-butyl, quizalofop-butyl, oxazolidinone, oxazolidinone, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, clodinafop-butyl, thiazolinone, clodinafop-butyl, chlorfenapyr, trifloxystrobin, isothiocarb, paraquat, diquat, oryzalin, ethylbutylfluanid, isopropylcarb, sulfenthiocarb, cyprodinil, aminopropylfluanid, ethylbutylfluanid, chloroethylfluanid, aminoethylfluanid, diclofenac, diclofenac, glyphosate, phosphamidon, glufosinate, methylaminophosphine, glufosinate-sulfate, phosphamidon, bialaphos, difenophos , imazaphos, cypermethrin, chlorpyrifos, dimethoate, chlorpyrifos, imazapic, imazapic, imazapic, chlorpyrifos ammonium, imazapic, imazapic, clofos-butyl, clofos-butyl, clofos-butyl, clofos-butyl, chlorpyrifos, chlorpyrifos-butyl ...Hexazinone, Metamitron, Ethylmetazolin, Ametridione, Amibuzin, Bromoxynil, Octanoyl Bromoxynil, Octanoyl Ioxyl, Ioxyl, Dichlobenil, Diphenylacetonitrile, Dipyridoxal, Hydroxypyridoxal, Iodobonil, Sulfursulfuron, Difluorosulfuron, Penoxsulam, Sulfursulfuron, Chlorosulfuron, Dichlorosulfuron, Pyroxypyramide, Fluorosulfuron, Bispyribac-butyl, Cyclopyramide, Pyroxypyramide, Pyroxypyramide, Bispyribac-butyl, Cyclopyramide, Pyroxypyramide, 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 pyraclostrobin, pyrazoline, fluazifop, sulfentrazone, Bencarbazone, bispyribac, fluazifop-butyl, bromocriptine, isothiocyanate, cypermethrin, cypermethrin, terclopyralid, Flupropacil, indolone, flumethoxal, fluazifop-butyl, cypermethrin, phthalein, Flumezin, pentachlorophenol (sodium), dinitrophenol, dinitrophenol, dinitrophenol, dioxin, dioxetone, oxadiazol, oxadiazol, cyclopentane Fluazifop, flumethoxam, fluazifop-butyl, tetrazolam, flupyridazone, herbicide-resistant, bromomyxin, dimethylpyridazone, pyridafol, quinclorac, quinmechlor, bentazon, pyridazone, oxaziclomefop, chlorpyrifos, isopropylpyridazone, cyproconazole, isopropylpyridazone, indole, sodium chlorate , dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, grass fast, bromophenol oxime, triazole sulfonate, methomyl, furochlor, furochlor, ethyl furochlor, chloranil, chlorthalid, fluchloralidone, barnyard grass, acrolein, benzylpyridinium chloride, benzylpyridinium chloride, avena sativa ester, thiadiazole, cotton amine, hydroxythiocarb, methoxybenzone, benzylpyridinium chloride, chloranil, trichloropropionic acid, Al orac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methylsulfuron, Cambendichlor, Cyprodinil, Thiencarbazone, Fenthiocyanate ...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. ,

[0055] When used, if necessary, commercially available formulations are diluted in a common manner, for example, in the case of wettable powders, concentrated emulsions, suspensions and granules 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 an inert substance before use. The required use amount of the compound of formula I varies with 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 substance, but preferably between 0.005 and 750 g ai / ha, particularly between 0.005 and 250 g ai / ha. DETAILED DESCRIPTION

[0056] The following examples are provided to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights claimed in the present invention is described in the claims.

[0057] Given the economical efficiency and diversity of the compounds, we have selected and synthesized a number of compounds. A selection of these compounds is listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are intended to better illustrate the present invention but are not intended to limit the present invention. Those skilled in the art should not interpret this as limiting the scope of the present invention to the following compounds.

[0058] Table 1 Compound structures and their 1 H NMR

[0059] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be understood 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 starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention that result in various isomerizations of the compounds are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups can be protected during the reaction, etc.

[0060] The following process examples are provided to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0061] Examples of representative compounds are shown below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0062] 1. Synthesis of Compound 1

[0063] 500 mg of 1-1 (1.0 eq) and 1-2 (1.2 eq) were added to a single-necked flask and dissolved in 10 mL of acetonitrile. DBU (1.5 eq) was then slowly added dropwise and allowed to react at room temperature for 10-30 min. Liquid chromatography-mass spectrometry (LC-MS) analysis indicated that the reaction was essentially complete. After the acetonitrile was dried, the residue was dissolved in DCM and washed three times with 1 M hydrochloric acid. The organic phase was dried over anhydrous sodium sulfate and then dried by spin drying. A trace amount of ethyl acetate was used to slurry the mixture to obtain 510 mg of pure solid product, Compound 1, in a 62% yield.

[0064] Biological activity evaluation:

[0065] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0066] Level 10: Complete death;

[0067] Level 9: Growth control rate is greater than or equal to 90% and less than 100%;

[0068] Level 8: Growth control rate is greater than or equal to 80% and less than 90%;

[0069] Level 7: Growth control rate is greater than or equal to 70% and less than 80%;

[0070] Level 6: Growth control rate is greater than or equal to 60% and less than 70%;

[0071] Level 5: Growth control rate is greater than or equal to 50% and less than 60%;

[0072] Level 4: Growth control rate is greater than or equal to 40% and less than 50%;

[0073] Level 3: Growth control rate is greater than or equal to 30% and less than 40%;

[0074] Level 2: Growth control rate is greater than or equal to 20% and less than 30%;

[0075] Level 1: Growth control rate is less than 20%;

[0076] Level 0: No effect.

[0077] The above growth control rates are fresh weight control rates.

[0078] Post-emergence test experiment:

[0079] Monocotyledonous and dicotyledonous weed seeds (artemisia selengensis, shepherd's purse, velvet, cleaver, chickweed, wheat family, sedge, alopecuroides, Japanese alopecuroides, goosegrass, sedge, hard grass, small flea market, candle grass, speedwell, brome, knotweed, phragmites, amaranth, quinoa, dayflower, sonchus, field bindweed, prickly lettuce, nightshade, amaranth, crabgrass, barnyard grass, foxtail grass, stephanotis, duck tongue grass, wild arrowhead, firefly rush, cyperus, cardamom, sedge, cyperus diversiformis, floating grass, purslane, cocklebur, 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 plastic pots filled with soil, covered with 0.5-2 cm of soil, and grown in a well-maintained greenhouse environment. Two weeks after sowing, at the 2-3 leaf stage, the test plants were treated. The test compound of the invention was dissolved in acetone, Tween 80 was added, and 1.5 L / hectare of methyl oleate emulsifiable concentrate was used as a synergist. The solution was diluted with water to a desired concentration and sprayed onto the plants using a spray tower. After three weeks of incubation in the greenhouse, the weed effects were analyzed. Compound dosages were 60, 15, and 7.5 g ai / ha, and the average value was calculated for three replicates. Representative data are listed in Table 2.

[0080] Table 2 Post-emergence weed test results

[0081] Note: N stands for no data; Reference compound A: Control compound B:

[0082] It can be seen from this that compound 1 of the present application is more active than the control compound, is safer for wheat, and has higher selectivity.

[0083] Pre-emergence test experiment:

[0084] Monocotyledonous and dicotyledonous weed seeds and major crop seeds (corn, wheat, rice, soybean, rapeseed, pepper, eggplant, potato, tobacco, cotton, flax, millet, sorghum, etc.) were placed in plastic pots filled with soil and then covered with 0.5-2 cm of soil. The test compounds of the present invention were dissolved in acetone, then Tween 80 was added and diluted with water to a certain concentration. The solution was sprayed immediately after sowing. After incubation in a greenhouse for 4 weeks after application, the experimental results were observed. It was found that most of the agents of the present invention were effective at a dosage of 60 g ai / ha, especially against weeds such as Amaranthus retroflexus, Abutilon, and Caulis chinensis. Many compounds also showed good selectivity against corn, wheat, rice, soybean, rapeseed, pepper, eggplant, potato, tobacco, cotton, flax, and sorghum.

[0085] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not limiting. 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 solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions 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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