Pyrimidine-substituted benzoxazinone compound, and preparation method therefor, weeding composition thereof and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a pyrimidine-substituted benzoxazinone compound, and a preparation method therefor, a weeding composition thereof and the use thereof. The compound is as shown in general formula I, wherein Q1 and Q2 independently represent O or S; X1 and X2 independently represent hydrogen, halogen, alkyl, etc.; Y represents hydrogen or halogen; Z represents hydrogen, alkyl, alkenyl, etc.; and R1, R2 and R3 independently represent hydrogen, halogen, alkyl, etc. The compound has excellent herbicidal activity and crop safety.

Description

Pyrimidine-substituted benzoxazinone compounds, preparation method thereof, herbicidal composition and application TECHNICAL FIELD

[0001] The present application belongs to the technical field of pesticides, and particularly relates to a pyrimidine-substituted benzoxazinone compound, a preparation method thereof, a herbicidal composition and application. BACKGROUND

[0002] The control of weeds is a crucial step in the process of achieving efficient agriculture. Although there are various types of herbicides on the market, the weed control performance of these known compounds on harmful plants and the selectivity to crops are not completely satisfactory. Due to the continuous expansion of the market, the resistance of weeds, the service life of drugs, the economy of drugs and the increasing attention to the environment, scientists need to continuously research and develop new herbicides with high efficiency, safety, economy and different modes of action. SUMMARY

[0003] The present application provides a pyrimidine-substituted benzoxazinone compound, a preparation method thereof, a herbicidal composition and application. The compound has excellent herbicidal activity and crop safety.

[0004] The technical scheme adopted by the present application is as follows:

[0005] A pyrimidine-substituted benzoxazinone compound or a salt thereof as shown in general formula I:

[0006] Q1 and Q2 independently represent O or S;

[0007] X1 and X2 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl; or X1 and X2 together form -CH2CH2- which is unsubstituted or substituted with halogen;

[0008] Y represents hydrogen or halogen;

[0009] Z represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -alkylene-OR, cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, aryl or arylalkyl;

[0010] R1, R2 and R3 independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyano, nitro, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl, heterocyclylalkyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -(CO)R or -(CO)N(R)2;

[0011] The aforementioned "cycloalkyl", "heterocyclyl" or "aryl" is optionally substituted with at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R;

[0012] R1, R2, R3, each independently, represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC1-C8 alkyl, haloC2-C8 alkenyl, haloC2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclyl, heterocyclylC1-C8 alkyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -(CO)R or -(CO)N(R)2;

[0013] In a particular embodiment, X1, X2, each independently, represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC1-C8 alkyl, haloC2-C8 alkenyl or haloC2-C8 alkynyl; or X1 and X2 together form -CH2CH2- unsubstituted or substituted by halogen;

[0014] Z represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC1-C8 alkyl, haloC2-C8 alkenyl, haloC2-C8 alkynyl, -OR, -(C1-C8 alkylene)-OR, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, heterocyclyl, heterocyclylC1-C8 alkyl, aryl or arylC1-C8 alkyl;

[0015] R1, R2, R3, each independently, represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC1-C8 alkyl, haloC2-C8 alkenyl, haloC2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclyl, heterocyclylC1-C8 alkyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -(CO)R or -(CO)N(R)2;

[0016] The aforementioned "C3-C8cycloalkyl", "heterocyclyl" or "aryl" is optionally substituted with at least one group selected from oxo, halogen, cyano, nitro, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, halogenated C1-C8alkyl, halogenated C2-C8alkenyl, halogenated C2-C8alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R;

[0017] R independently represents hydrogen, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl substituted with at least one group selected from halogen, hydroxy, C1-C8alkoxy, cyano or C1-C8alkyloxy carbonyl, C3-C8cycloalkyl, C3-C8cycloalkyl C1-C8alkyl, C3-C8cycloalkenyl, C3-C8cycloalkenyl C1-C8alkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8alkyl, halogenated C1-C8alkyl, C1-C8alkyloxy carbonyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy or halogenated C1-C8alkoxy.

[0018] In another embodiment, X1, X2independently represent hydrogen, halogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, halogenated C1-C6alkyl, halogenated C2-C6alkenyl or halogenated C2-C6alkynyl; or X1and X2together form -CH2CH2- unsubstituted or substituted with halogen.

[0019] In another embodiment, Z represents hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, halogenated C1-C6alkyl, halogenated C2-C6alkenyl, halogenated C2-C6alkynyl, -OR, -(C1-C6alkylene)-OR, C3-C6cycloalkyl, C3-C6cycloalkyl C1-C6alkyl, heterocyclyl, heterocyclyl C1-C6alkyl, aryl or aryl C1-C6alkyl.

[0020] In another embodiment, R1, R2, R3independently represent hydrogen, halogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, halogenated C1-C6alkyl, halogenated C2-C6alkenyl, halogenated C2-C6alkynyl, cyano, nitro, C3-C6cycloalkyl, C3-C6cycloalkyl C1-C6alkyl, aryl, aryl C1-C6alkyl, heterocyclyl, heterocyclyl C1-C6alkyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -(CO)R or -(CO)N(R)2.

[0021] In another embodiment, the aforementioned "C3-C6cycloalkyl", "heterocyclyl" or "aryl" is optionally substituted with at least one group selected from oxo, halogen, cyano, nitro, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, halogenated C1-C6alkyl, halogenated C2-C6alkenyl, halogenated C2-C6alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R.

[0022] In another embodiment, R independently represents hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkylC1-C6alkyl, C3-C6cycloalkenyl, C3-C6cycloalkenylC1-C6alkyl, phenyl or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6alkyl, halogenated C1-C6alkyl, C1-C6alkoxycarbonyl, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkoxy or halogenated C1-C6alkoxy.

[0023] In the definitions of the compounds of the general formulae above and in all the formulae below, the terms used, whether used alone or in a compound word, represent the following substituents: Alkyl groups having more than two carbon atoms can be straight-chain or branched. As in the compound word "cycloalkylalkyl" the alkyl groups can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. Alkyl groups are, for example, C1alkyl - methyl; C2alkyl - ethyl; C3alkyl - propyl, such as n-propyl or isopropyl; C4alkyl - butyl, such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5alkyl - pentyl, such as n-pentyl; C6alkyl - hexyl, such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl is, for example, ethenyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. The multiple bonds can be in any position of each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl group having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein the double bonds can be in any position. Halogen is fluorine, chlorine, bromine or iodine.

[0024] Unless specifically indicated otherwise, "aryl" as used in the present application includes, but is not limited to, phenyl, naphthyl, "Heterocyclyl" as used herein includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups "Heterocyclyl" as used herein includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups

[0025] The term "optionally" or "optional" means that the subsequently described event or circumstance can or can not occur, and thus describes instances where the event or circumstance occurs and instances where it does not. For example, the term "optionally substituted" means that the specified atom or group is either unsubstituted or substituted with one or more substituents. If a group is substituted with a group, this is to be understood as meaning that the group is substituted with one or more, identical or different, groups selected from those mentioned. In addition, the same or different substituents contained in the same or different substituent groups are each selected independently of one another, either identically or differently. This also applies to ring systems formed by different atoms and elements. At the same time, the scope of the claims is to exclude those compounds which are chemically unstable under standard conditions, as known to the person skilled in the art.

[0026] In addition, unless specifically limited otherwise, the term "substituted" as used herein means substituted with one, two, three, four or five groups; groups (including heterocyclyl, aryl, etc.) not marked with a specific position of attachment can be attached at any position, including the position of attachment to C or N; if it is substituted, the substituents can likewise be substituted at any position, as long as the rules of chemical bonding are followed. For example, a heteroaryl group may represent etc.

[0027] If various functional groups are present, the application also includes any keto and enol tautomeric forms and mixtures and salts thereof.

[0028] Stereoisomers can be obtained from mixtures obtained in the preparation by optical resolution. Stereoisomers can likewise be prepared selectively by using stereoselective reactions and using optically active starting materials and / or auxiliaries. For optical resolution, it is generally possible to employ conventional methods (cf. Textbooks of Stereochemistry), for example the following methods for the resolution of mixtures into diastereomers: physical methods such as crystallization, chromatography, in particular column chromatography and high-pressure liquid chromatography, distillation methods, which are carried out if appropriate under reduced pressure, extraction and other methods, usually with chromatographic separation on chiral stationary phases, which make it possible to separate the residual mixtures of enantiomers. Suitable for preparative amounts or for industrial scale are methods such as crystallization of diastereomeric salts, which can be obtained from the compounds using optically active acids and, if acidic groups are present, if appropriate using optically active bases.

[0029] The preparation method of the one pyrimidine substituted benzoxazinone compound comprises the following steps:

[0030] (1) the compound shown in general formula II is reacted with the compound shown in general formula III to prepare the compound shown in general formula I, and the reaction equation is as follows:

[0031] (2) the compound represented by general formula IV is condensed to prepare the compound represented by general formula I, and the reaction equation is as follows:

[0032] Alternatively, (3) the compound represented by general formula I' reacts with Hal-Z' to prepare the compound represented by general formula I", and the reaction equation is as follows:

[0033] wherein Hal represents halogen, either of P1 and P2 is halogen, and the other is Z' represents a group Z other than hydrogen, and the definitions of other substituents Q1, Q2, X1, X2, R1, R2, R3, Y and Z are as described above.

[0034] In one specific embodiment, the reaction (1) is carried out in the presence of a base, a catalyst and a solvent.

[0035] In one specific embodiment, the catalyst is at least one selected from Pd(dppf)Cl2, Pd(dppf)Cl2·CH2Cl2, Pd(OAc)2, PdCl2, Pd(PPh3)4 or PdCl2(PPh3)2.

[0036] In one specific embodiment, the solvent is an organic solvent or a mixture thereof with water (the volume ratio of the two is preferably 20 / 1-1 / 1), and the organic solvent is dioxane, toluene, DMF or DMSO.

[0037] In one specific embodiment, the reactions (2) and (3) are carried out in the presence of a base and a solvent.

[0038] In one specific embodiment, the base is at least one selected from an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KI, NaI, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, NaH, KH, etc.) or an organic base (such as DMAP, pyrazole, triethylamine, DIEA, etc.).

[0039] In one specific embodiment, the solvent is at least one selected from aromatic hydrocarbons (such as benzene, chlorobenzene or toluene), DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, toluene or ethyl acetate.

[0040] In addition, the compound of the present application can be prepared by referring to the method shown in CN201180054676.3 and the like.

[0041] An intermediate, such as shown in Formula II or IV.

[0042] A herbicidal composition comprising a herbicidally effective amount of at least one of the pyrimidine-substituted benzoxazinone compounds described; preferably, further comprising formulation adjuvants; more preferably, further comprising other active ingredients.

[0043] A method of controlling weeds comprising applying a herbicidally effective amount of at least one of the pyrimidine-substituted benzoxazinone compounds described or the herbicidal composition described to a plant or to an area of weeds.

[0044] Use of at least one of the pyrimidine-substituted benzoxazinone compounds described or the herbicidal composition described for controlling weeds, preferably, use of the pyrimidine-substituted benzoxazinone compounds for controlling weeds in transgenic crops or crops treated by genome editing technology.

[0045] The compounds of the formula I of the present application have outstanding herbicidal activity against many economically important monocotyledonous and dicotyledonous harmful plants. The active substances of the present application are also effective against perennial weeds which grow from rhizomes, tubers or other perennial organs and are difficult to control. In this connection, it is generally immaterial whether the substances are used before sowing, before germination or after germination. Particular mention comes to representatives of the group of monocotyledonous and dicotyledonous weeds which can be controlled by the compounds of the present application without limitation to the specified species. Examples of weed species against which the active substances are effective include the following monocotyledons: annuals of the genera Avena, Secale, Phalaris, Alopecurus, Setaria, Eleusine, Digitaria, Cynodon and Cyperus, and the perennials of the genera Agropyron, Cynodon, Imperata and Sorghum, and the perennial Cyperus.

[0046] As regards the dicotyledonous weed species, the activity can extend to species such as annuals of the genera Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Raphanus, Ipomoea, Sida, Matricaria and Abutilon, and the perennials of the genera Convolvulus, Cirsium, Rumex and Artemisia. The active substances of the present application are effective in controlling harmful plants under the conditions prevailing at the time of sowing of rice, for example, in the case of Setaria, Sagittaria, Alisma, Alocasia, Sorghum and Cyperus. If the compounds of the present application are applied to the soil surface before germination, the seedlings of the weeds can be completely prevented from growing before the weeds emerge, or growth can be stopped at the time of emergence of the cotyledons, and finally complete death can occur after three to four weeks. The activity of the compounds of the present application is particularly good against the following plants, Apluda, Lamium, Polygonum, Stellaria, Hedera helix, Veronica arvensis, Veronica persica, Viola tricolor and Amaranthus, Galium and Kochia.

[0047] While the compounds according to the application have excellent herbicidal activity against mono- and dicotyledonous weeds, they have no or only negligible damage to important economic crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. In particular, they are very well compatible with cereal crops, such as wheat, barley and maize, in particular wheat. Thus, the compounds according to the application are very suitable for the selective control of unwanted plants in crops of useful plants or ornamentals.

[0048] Due to their herbicidal properties, the active substances can be used for controlling harmful plants in genetically modified plants which are known or will be developed in the future. Genetically modified plants typically have superior traits, such as resistance to specific pesticides, in particular to specific herbicides, resistance to plant diseases or to disease-causing microorganisms of plants, such as specific insects or fungi, bacteria or viruses. Other specific traits are related to the product, such as quantity, quality, storage stability, components and special ingredients. Thus, it is known to obtain genetically modified plant products with increased starch content or improved starch quality or different fatty acid composition.

[0049] The compounds of the formula I according to the application or their salts are preferably used in the cultivation of genetically modified crop plants and ornamentals of economic importance, such as cereals, for example wheat, barley, rye, oats, millet, rice, cassava and maize, or in the cultivation of sugar beet, cotton, soybean, rapeseed, potato, tomato, peas and other vegetable plants. The compounds of the formula I are preferably used as herbicides in the cultivation of useful plants which are resistant to herbicides or which have been rendered resistant to the harmful effects of herbicides by genetic engineering.

[0050] Traditional methods of breeding plants with improved properties compared to known plants include, for example, traditional crossbreeding methods and breeding of mutants. In other words, new plants with improved properties can be obtained by means of methods of genetic engineering (cf., for example, EP-0221044A, EP-0131624A). For example, several methods have been described:

[0051] - for improving starch synthesis in plants, crop plants are modified by genetic engineering (for example WO 92 / 11376, WO 92 / 14827, WO 91 / 19806);

[0052] - transgenic crop plants which are resistant to specific herbicides, such as herbicides based on glufosinate (for example EP-0242236A, EP-0242246A) or on glyphosate (WO 92 / 00377) or on sulfonylurea herbicides (EP-0257993A, US-5013659A);

[0053] - transgenic crop plants, for example of cotton, which are capable of producing a toxin of Bacillus thuringiensis (Bt toxin) which protects the plants from certain pests (EP-0 142 924 A, EP-0 193 259 A);

[0054] - transgenic crop plants with improved fatty acid composition (WO 91 / 13972).

[0055] Numerous molecular biological techniques are known which make it possible to prepare transgenic plants with improved properties (cf., for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2ndEdition, Cold Spring Harbor Laboratory, Cold Spring Harbor, New York; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2ndEdition 1996 or Christou, Trends in Plant Science 1 (1996) 423-431)). In order to achieve the genetic engineering manipulations, it is possible to introduce nucleic acid molecules into plasmids, to mutate or to change sequences by recombination of DNA sequences. Using the standard methods described above, it is possible, for example, to exchange substrates, to remove partial sequences or to add natural or synthetic sequences. In order to join DNA fragments to one another, it is possible to attach linkers or adaptors to the fragments.

[0056] It is possible to prepare plant cells with reduced activity of a gene product, for example by expressing at least one suitable antisense-RNA, sense-RNA to achieve cosuppression, or by expressing at least one suitably constructed ribozyme which specifically cleaves the transcript of the gene product in question.

[0057] For this purpose, it is possible to use DNA molecules which comprise the entire coding sequence of the gene product, including any flanking sequences which can be present, and DNA molecules which comprise only a part of the coding sequence, which part must be sufficiently long to achieve antisense effects in the cell. It is also possible to use sequences which have a high degree of homology with the coding sequence of the gene product but are not identical.

[0058] When nucleic acid molecules are expressed in plants, the synthesized proteins can be localized in any desired plant cell compartment. However, in order to be localized in a particular compartment, it is possible, for example, to link the coding region and DNA sequences which ensure localization in a particular location. These sequences are known to the person skilled in the art (cf., for example, Braun et al., EMBO J. 11 (1992) 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 65 (1988), 846-850; Sonnewald et al. Plant J. 1 (1991), 95-106).

[0059] The transgenic plant cells can be recombined into whole plants using known techniques. The transgenic plants can be any desired plant species, i.e. monocotyledonous and dicotyledonous plants. In this way, by overexpression, inhibition or suppression of homologous (= natural) genes or gene sequences, or by expression of heterologous (= foreign) genes or gene sequences, it is possible to obtain transgenic plants with improved properties.

[0060] When the active substances according to the application are used on transgenic crops, in addition to the effect observed on other crops of inhibiting harmful plants, there is often a special effect on the corresponding transgenic crop, for example it is possible to improve or extend the spectrum of weed control, to improve the application rate at the time of application, to combine the preferred resistance of the transgenic crop to the herbicide with good herbicidal properties, and to influence the growth and yield of the transgenic crop plant. The use of the compounds according to the application as herbicides for controlling harmful plants in transgenic crop plants is therefore also provided.

[0061] In addition, the compounds according to the application can significantly influence the growth of the crop plants. By influencing the metabolism of the plants, it is possible to direct the components of the plants using these compounds and to promote the harvest, for example to dry and stunt the growth of the plants. Furthermore, they are suitable for regulating and inhibiting the growth of unwanted plants without destroying the growth of the crop. Inhibition of the growth of the plants plays a very important role in many monocotyledonous and dicotyledonous crop plants, since it is possible to reduce or completely prevent lodging.

[0062] The compounds of the present application can be applied using the usual formulations, using wettable powders, emulsifiable concentrates, sprayable solutions, powders or granules. The present application thus also provides herbicidal compositions comprising a compound of formula I. The compounds of formula I can be formulated in various ways depending on the usual biological and / or chemical-physical parameters. Examples of suitable formulation types are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil dispersions, sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions in oil or water, solutions of miscible oils, powders (DP), capsule suspensions (CS), seed dressing compositions, granules for broadcasting and for soil application, injection granules, coating granules and absorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (ultra low volume) formulations, microencapsulations and waxes. These individual formulation types are known and are described, for example, in Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd edition 1979, G. Goodwin Ltd. London.

[0063] The necessary formulation adjuvants, such as inert substances, surfactants, solvents and other additives, are likewise known and are described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd edition, Darland Books Caldwell N.J.; H. v. 01 phen, "Einfuhrung in die Kolloidchemie", 2nd edition, J. Wiley and Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd edition, Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., N.Y. 1964; [Oxirane adduct surfactants], Wiss. Verlagagesell. Stuttgart 1976; Winnacker- ​"Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th edition 1986.

[0064] Wettable powders are uniformly dispersible in water and comprise, in addition to the active substances, diluents or inert substances, ionic and non-ionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethyl fatty amines, fatty alcohol polyglycol ether sulphates, alkylsulphonates, alkylphenylsulphonates, sodium lignosulphonate, sodium 2,2'-dinaphthylmethane-6,6'-disulphonate, sodium dibutylnaphthalenesulphonate or sodium oleylmethyltaurinate. To prepare wettable powders, the active substances of the herbicides are finely ground, for example using customary apparatuses, such as hammer mills, fan mills and jet mills, and the adjuvants are mixed in simultaneously or sequentially.

[0065] Concentrated emulsions are prepared by dissolving the active substances in organic solvents, such as butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatic or hydrocarbon compounds or mixtures of solvents, and adding one or more ionic and / or non-ionic surfactants (emulsifiers) thereto. Examples of emulsifiers which can be used are, for example, calcium alkylaryl sulphonates, such as calcium dodecylbenzenesulphonate, or non-ionic 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 esters.

[0066] Powders are obtained by grinding the active substances with finely divided solid substances, such as talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspensions, based on water or oils, can be prepared by wet grinding, for example using commercially customary bead mills, with or without addition of surfactants of another type of formulation as described above.

[0067] Emulsions, such as oil-in-water emulsions (EW), are prepared using aqueous organic solvents, using stirrers, colloid mills and / or static mixers, if desired, with the addition of surfactants of another type of formulation as described above.

[0068] Granules are prepared by spraying the active material onto an adsorbent, granulating with inert material, or by concentrating the active material onto the surface of a carrier such as sand, kaolin, granulating with an inert material by means of a binder such as polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active materials can be granulated using methods known for the preparation of granules for fertilizers, if desired in admixture with fertilizers. Water-suspension granules are prepared using customary methods, for example spray-drying, fluidized-bed granulation, pan granulation, mixing using a high-speed mixer and extrusion without solid inert material.

[0069] For the preparation of granules using pan, fluidized-bed, extruder and spray methods, reference is made to the processes described, for example, in the "Spray Drying Handbook", 3rdEdition 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook", 5thEdition, McGraw-Hill, New York 1973, pages 8-57. For information on the formulation of crop protection products, reference is made, for example, to G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York 1961, pages 181-96 and J. D. Freyer, S. A. Evans, "Weed Control Handbook", 5thEdition, Blackwell Scientific Publications, Oxford 1968, pages 101-103.

[0070] The agrochemical formulations usually contain 0.1 to 99 %, in particular 0.1 to 95 %, by weight, of the active substance of the formula I. The concentration of the active substance in wettable powders is, for example, from about 10 to 99 %, the remainder to 100 % by weight consisting of customary formulation components. The concentration of the active substance in emulsifiable concentrates can be from about 1 to 90 %, preferably from 5 to 80 %, by weight. Dustable powders contain from 1 to 30 %, usually preferably from 5 to 20 %, by weight, of the active substance, whereas sprayable solutions contain from about 0.05 to 80 %, preferably from 2 to 50 %, by weight, of the active substance. The content of active substance in water-suspension granules depends mainly on whether the active substance is liquid or solid and on the auxiliaries, fillers, etc. used in the granulation. The content of active substance in water-suspension granules is, for example, between 1 and 95 %, preferably between 10 and 80 %, by weight.

[0071] The formulations described additionally can comprise tackifiers, wetting agents, dispersants, emulsifiers, penetration agents, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and, in general, pH and viscosity regulators which are customary in each case.

[0072] On the basis of these formulations, it is also possible to mix with other pesticidally active substances, such as insecticides, acaricides, herbicides and fungicides, but also with safeners, fertilizers and / or plant growth regulators, either in the form of ready-to-use mixtures or in the form of tank mixes.

[0073] 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,Sapro- leine, Fluometuron, Benzthiazuron, Methabenzthiazuron, Bensulide, Thiaza- furon, Triazifluron, Tebutam, Clofuron, Methyldymron, Profoxydim, Dymron, Methoxy- prop, Greenall, Monuron, Cybutryne, Fluothiuron, Siduron, Triflu- ron, Esprocarb, Espro- carb-ethyl, EPTC, Bentazon, Dimethamethryn, Dimethamethryn-ethyl, Bifenox, Aciflu- ceton, Benfluralin, Butachlor, Propanil, Chlorprocarb, Fenasulam, BCPC, CPPC, Car- basulam, Butachlor, Propanil, Alachlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met- olachlor, Sulfentrazone, Acetochlor, Metolachlor, Sulfentrazone, Acetochlor, Met-Hexazinone, Metamitron, Ethylmetribuzin, Ametridione, Amibuzin, Bromoxynil, Octanoyl Bromoxynil, Octanoyl Ioxyl, Ioxyl, Dichlobenil, Diphenylacetonitrile, Dipyridamole, Hydroxypyridamole, 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, Me Thiozolin, isopropylpyraclostrobin, pyrasulfobutyl, pyrazoline, wild yanquat, benzylpyrazone, pyrasulfotole, pyroxasulfone, pyrasulfobutyl, fluazifop, chlorfenapyr, fenpyrazone, fluazifop, sulfentrazone, bencarbazone, fluazifop-butyl, bromocriptine, isothiocyanate, cypermethrin, cypermethrin, terclopyralid, flupropacil, flupropacil, flufenacet, fluazifop-butyl, clofosamide, phthalein, flumezin, pentachlorophenol (sodium), dinoseb, teroseb, terosebate, pentachlorophenol, dinitrophenol, chlorfenapyr, dinoseb, teroseb, oxadiazol, oxadiazol, cyclopentadiazol , fluazifop-butyl, fluazifop-butyl, tetrazolam, fluazifop-butyl, herbicide-resistant, bromomyxin, dimethylpyridasulfuron, pyridafol, chlorfenapyr, chlorfenapyr, chlorfenapyr, pyridafol, quinclorac, chlormequat, bentazon, pyridasulfuron, oxaziclomefop-butyl, chlorfenapyr, isopropylpyridasulfuron, chlorfenapyr, sodium chlorate, thatch Cetirizine, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, bromophenol oxime, triazole sulfonate, methomyl, furazolidone, furazolidone, ethylfuransulfonate, chloranil, chlorthalidone, fluazifop, barnyardgrass, acrolein, benzylpyridinium chloride, benzylpyridinium chloride, avena sativa ester, thiadiazole, cotton amine, hydroxythiocarb, methoxybenzone, benzylpyridinium chloride, chloranil, trichloropropionic acid, Alora c、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、Methylsulfuron、Cambendichlor、Cyclopropane、Thiocyananilide、Fenthiocarbazone、Fenthiocarbazone、Fenthiocarbazone-methyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、Methiosulfuron、Cambendichlor、Cyclopropane ...LS82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO 535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.

[0074] When used, commercially available formulations are diluted, if necessary, in the usual manner, for example with water in the case of wettable powders, emulsifiable concentrates, suspensions and granules which are suspended in water. Powders, granules for soil application or solutions for spreading and spraying generally do not require further dilution with inert substances before use. The amount of the compound of formula I to be used varies as a function of external conditions, for example temperature, humidity, nature of the herbicide used, etc. It can vary within wide limits, for example between 0.001 and 1.0 kg a.i. / ha, or more of active substance, but is preferably between 0.005 and 750 g a.i. / ha, in particular between 0.005 and 250 g a.i. / ha. DETAILED DESCRIPTION

[0075] The following examples are intended to illustrate the present application and should not be construed as limiting the application in any way. The scope of the application claimed is set forth in the claims. In view of the economics and diversity of compounds, we have synthesized a number of compounds, of which a selection is listed in Tables 1-2 below. The structures of the specific compounds and the corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustrating the present application, but do not limit the present application, and for those skilled in the art, this should not be understood as the scope of the above-mentioned subject matter of the present application is limited to the following compounds.

[0076] Table 1 Compound Structures

[0077] Table 2 Compounds 1 HNMR

[0078] Several methods for preparing the compounds of the present application are illustrated in the following Schemes and Examples. Starting materials can be purchased from vendors or can be prepared by known methods in the literature or as illustrated. Those skilled in the art will appreciate that other synthetic routes can be used to synthesize the compounds of the present application. Although specific starting materials and conditions are depicted in the schemes below, other suitable starting materials and conditions can be readily adapted and are included in the present application. In addition, the synthetic methods described below can be further modified to produce additional compounds of the present application using conventional chemistry as known to those skilled in the art.

[0079] The following method examples are provided to further illustrate the preparation of the compounds of the present application and are not intended to limit the scope of the application. The reagents used in the synthesis of the compounds shown in the following table are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0080] Representative compounds are prepared as follows, and other compounds are prepared in a similar manner.

[0081] 1. Synthesis of compound 41

[0082] (1) Compound 41-1 (3.0 g, 16.5 mmol), 41-2 (3.4 g, 19.8 mmol), potassium carbonate (6.8 g, 49.5 mmol) were dissolved in 20 mL of 1,4-dioxane and 2 mL of water, and a catalytic amount of 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride was added. The reaction was stirred at 100 °C under nitrogen for 12 hours. The reaction was monitored by LCMS and was complete. The reaction was concentrated and diluted with ethyl acetate. The organic phase was washed with water and saturated brine, dried and concentrated. The residue was purified by column chromatography to give 41-3 (2.9 g, 64.6% yield) as a light yellow oil.

[0083] (2) Compound 41-3 (2.9 g, 10.7 mmol) was dissolved in 20 mL of concentrated sulfuric acid, and nitric acid (674 mg, 10.7 mmol) was added at 0 °C. The reaction was stirred at room temperature for 1 hour. The reaction was monitored by LCMS and was complete. The reaction was poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, dried and concentrated. The residue was purified by column chromatography to give 41-4 (3.1 g, 91.4% yield) as a yellow oil.

[0084] (3) Compound 41-4 (3.1 g, 9.8 mmol) was dissolved in 18 mL of ethanol and 6 mL of water, and iron powder (2.7 g, 49 mmol) and ammonium chloride (2.6 g, 49 mmol) were added at room temperature, and stirred at 80°C for 2 hours. The reaction was monitored by LCMS, and when the reaction was completed, the reaction solution was filtered with diatomite while hot, and the filtrate was diluted with ethyl acetate. The organic phase was washed with water and saturated brine, dried and concentrated. The residue was purified by column chromatography to obtain Compound 41-5 (2.7 g, yield 96%) as a yellow solid.

[0085] (4) Compound 41-5 (2.7 g, 9.4 mmol) was dissolved in 20 mL of dichloromethane, and boron tribromide (4.7 g, 18.8 mmol) was added dropwise at 0°C, and stirred at room temperature for 4 hours. The reaction was monitored by LCMS, and when the reaction was completed, the reaction solution was poured into ice water, and extracted with dichloromethane. The organic phase was washed with water and saturated brine, dried and concentrated. The residue was purified by column chromatography to obtain Compound 41-6 (1.7 g, yield 66.2%) as a yellow solid.

[0086] (5) Compound 41-6 (200 mg, 0.73 mmol) was dissolved in 5 mL of tetrahydrofuran, and sodium hydride (58 mg, 0.88 mmol) was added at 0°C. After stirring for 0.5 hours, Compound 41-7 (300 mg, 1.47 mmol) was added to the reaction solution, and stirred at room temperature for 2 hours. The reaction was monitored by LCMS, and when the reaction was completed, the reaction solution was added to ice water, and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, dried and concentrated to obtain Compound 41-8 as a yellow oil, which was directly used in the next reaction.

[0087] (6) Compound 41-8 (313 mg, 0.73 mmol) was dissolved in 10 mL of DMF, and potassium carbonate (302 mg, 2.2 mmol) was added at 0°C. The reaction was stirred at 80°C for 12 hours. The reaction was monitored by LCMS, and when the reaction was completed, the reaction solution was diluted with ethyl acetate. The organic phase was washed with water and saturated brine, dried and concentrated to obtain Compound 41-9 as a yellow oil, which was directly used in the next reaction.

[0088] (7) Compound 41-9 (255 mg, 0.73 mmol) was dissolved in 5 mL of DMF, and 41-10 (174 mg, 1.46 mmol) and potassium carbonate (302 mg, 2.19 mmol) were added at 0°C. The reaction was stirred at room temperature for 12 hours. The reaction was monitored by LCMS, and when the reaction was completed, the reaction solution was diluted with ethyl acetate. The organic phase was washed with water and saturated brine, dried and concentrated. The residue was purified by column chromatography to obtain Compound 41 (34 mg, yield 12%) as a white solid.

[0089] 2. Synthesis of compound 47

[0090] (1) Compound 47-1 (0.3 g, 1.22 mmol), compound 47-2 (0.47 g, 1.83 mmol), potassium acetate (0.36 g, 3.66 mmol) were dissolved in 10 mL of 1,4-dioxane, and a catalytic amount of 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride was added. The system was stirred at 100 °C under nitrogen overnight. LCMS was used to monitor the completion of the reaction, and the reaction system was directly used in the next step.

[0091] (2) Compound 41-1 (0.34 g, 1.84 mmol), cesium fluoride (0.56 g, 3.67 mmol), and water (1 mL) were added to the reaction system of the previous step, and a catalytic amount of 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride was added. The system was stirred at 100 °C under nitrogen overnight. LCMS was used to monitor the completion of the reaction, and the reaction liquid was concentrated. The residue was purified by column chromatography to obtain compound 47-4 (0.16 g, yield 74%) as a light yellow oil.

[0092] (3) Compound 47-4 (0.16 g, 0.51 mmol) was dissolved in 5 mL of DMF, and potassium carbonate (0.22 g, 1.53 mmol) and 41-10 (0.09 g, 0.76 mmol) were added. The system was stirred at 45 °C overnight. Ethyl acetate was added for dilution, and the organic phase was washed with water and saturated brine. After drying and concentration, the residue was purified by column chromatography to obtain compound 47 (56 mg, yield 40%) as a light yellow solid.

[0093] 3. Synthesis of compound 81

[0094] (1) Compound 81-1 (0.50 g, 1.00 eq) was dissolved in 8 mL of ACN, and 3-bromopropene (0.35 g, 1.50 eq) and K2CO3 (0.75 g, 3.00 eq) were added. The system was heated to 80 °C and reacted overnight. Extraction was performed with EA and H2O, the organic phase was collected, dried over anhydrous sodium sulfate, and then purified by normal phase to obtain compound 81-2 (0.40 g, yield 80%) as a brown solid.

[0095] (2) Compound 81-2 (0.40 g, 1.00 eq) was dissolved in 8 mL of dioxane, 47-2 (0.38 g, 1.2 eq), potassium acetate (0.37 g, 3 eq) and 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride dichloromethane complex (0.05 g, 0.05 eq) were added, the system was raised to 100 °C, and the reaction was carried out for 16 h. The system was directly rotary evaporated to remove the solvent, and used in the next step.

[0096] (3) Compound 81-3 (0.40 g, 1.00 eq) was dissolved in 10.0 mL of dioxane: water = 10: 1 mixed solvent, 81-4 (0.28 g, 1.2 eq), 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride dichloromethane complex (0.056 g, 0.05 eq) and potassium carbonate (0.41 g, 3 eq) were added, the system was raised to 100 °C, and the reaction was carried out for 16 h. EA and H2O were used for extraction, the organic phase was collected, dried over anhydrous sodium sulfate, stirred, and purified by normal phase to obtain brown solid compound 81 (0.01 g, yield 25%).

[0097] Biological activity evaluation:

[0098] The activity level criteria for plant destruction (i.e., growth control rate) are as follows:

[0099] 9: complete death;

[0100] 8: growth control rate greater than or equal to 90% and less than 100%;

[0101] 7: growth control rate greater than or equal to 80% and less than 90%;

[0102] 6: growth control rate greater than or equal to 70% and less than 80%;

[0103] 5: growth control rate greater than or equal to 50% and less than 70%;

[0104] 4: growth control rate greater than or equal to 30% and less than 50%;

[0105] 3: growth control rate greater than or equal to 20% and less than 30%;

[0106] 2: growth control rate greater than or equal to 10% and less than 20%;

[0107] 1: growth control rate less than 10%;

[0108] 0: no effect.

[0109] The above growth control rate is fresh weight control rate.

[0110] Post-emergence test experiment:

[0111] The seeds of monocotyledonous and dicotyledonous weeds and the seeds of main crops were placed in plastic pots filled with soil, and then covered with 0.5-2 cm of soil, and the test plants were treated at the 2-5 leaf stage after 2 weeks of sowing. The test compounds of the present application were dissolved in acetone, and then Tween 80 was added, and 1.5 L / ha of methyl oleate emulsion was added as a synergist, and then diluted with water to a certain concentration, and then sprayed onto the plants using a spray tower. After 2-3 weeks of culture in the greenhouse after application, the test results of weeds were counted, and representative data are shown in Table 3.

[0112] Table 3 Post-emergence test experiment results Note: N represents no data.

[0113] Pre-emergence test experiment:

[0114] The seeds of monocotyledonous and dicotyledonous weeds and the seeds of main crops were placed in plastic pots filled with soil, and then covered with 0.5-2 cm of soil, and the test compounds of the present application were dissolved in acetone, and then Tween 80 was added, and then diluted with water to a certain concentration, and then sprayed immediately after sowing. After 3 weeks of culture in the greenhouse after application, the test results were observed, and representative data are shown in Table 4.

[0115] Table 4 Pre-emergence test experiment results Note: N represents no data.

[0116] At the same time, it was found through many tests that the compounds and compositions of the present application can prevent many key grass weeds, broadleaf weeds, and sedge weeds, etc., and show excellent commercial value.

[0117] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present application can be modified or replaced equivalently without departing from the spirit and scope of the technical solutions of the present application.

Claims

1. A pyrimidine-substituted benzoxazinone compound of the formula I: ###00001### or a salt thereof. ​ Q1, Q2 each independently represent O or S; X1, X2 each independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl; or X1and X2together form -CH2CH2- which is unsubstituted or substituted by halogen; Y represents hydrogen or halogen; Z represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -alkylene-OR, cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, aryl or arylalkyl; R1, R2, R3 each independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyano, nitro, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl, heterocyclylalkyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -(CO)R or -(CO)N(R)2; the aforementioned "cycloalkyl", "heterocyclyl" or "aryl" is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R or -(SO2)R; R each independently represents hydrogen, alkyl, alkenyl, alkynyl, alkyl, alkenyl or alkynyl substituted by at least one group selected from halogen, hydroxy, alkoxy, cyano or alkoxycarbonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

2. The pyrimidine-substituted benzoxazinone compound according to claim 1, characterized in that, X1, X2 each independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC1-C8 alkyl, haloC2-C8 alkenyl or haloC2-C8 alkynyl; or X1and X2together form -CH2CH2- which is unsubstituted or substituted by halogen; Z represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC1-C8 alkyl, haloC2-C8 alkenyl, haloC2-C8 alkynyl, -OR, -(C1-C8 alkylene)-OR, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, heterocyclyl, heterocyclylC1-C8 alkyl, aryl or arylC1-C8 alkyl; R1, R2, R3 each independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, cyano, nitro, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, aryl, aryl-C1-C8 alkyl, heterocyclyl, heterocyclyl-C1-C8 alkyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -(CO)R, or -(CO)N(R)2; the aforementioned "C3-C8 cycloalkyl", "heterocyclyl", or "aryl" is optionally substituted with at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R; R each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl substituted with at least one group selected from halogen, hydroxy, C1-C8 alkoxy, cyano, or C1-C8 alkoxycarbonyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl-C1-C8 alkyl, phenyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy, or halo-C1-C8 alkoxy. 3.The pyrimidine-substituted benzoxazinone compound according to claim 1, characterized in that, X1, X2 each independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, or halo-C2-C6 alkynyl; or X1 and X2 together form -CH2CH2- which is unsubstituted or substituted with halogen; Z represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, -OR, -(C1-C6 alkylene)-OR, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, heterocyclyl, heterocyclyl-C1-C6 alkyl, aryl, or aryl-C1-C6 alkyl; R1, R2, R3 independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, cyano, nitro, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, aryl, aryl-C1-C6 alkyl, heterocyclyl, heterocyclyl-C1-C6 alkyl, -OR, -SR, -SOR, -(SO2)R, -N(R)2, -(CO)R, or -(CO)N(R)2; the aforementioned "C3-C6 cycloalkyl", "heterocyclyl", or "aryl" is optionally substituted with at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, -OR, -SR, -(CO)R, -(CO)OR, -(CO)N(R)2, -(CS)N(R)2, -(SO)R, or -(SO2)R; R independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl substituted with at least one group selected from halogen, hydroxy, C1-C6 alkoxy, cyano, or C1-C6 alkoxycarbonyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl-C1-C6 alkyl, phenyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy, or halo-C1-C6 alkoxy; Preferably, the compound is selected from any one of Table 1 of the specification.

4. A process for the preparation of the pyrimidine-substituted benzoxazinone compound according to any one of claims 1-3, comprising the steps of: (1) The compound of formula II is reacted with the compound of formula III to produce the compound of formula I, as shown in the following reaction equation: (2) The compound represented by general formula I is prepared by condensation reaction from the compound represented by general formula IV, and the reaction equation is as follows: Alternatively, (3) the compound of general formula I" is prepared by reacting the compound of general formula I' with Hal-Z', according to the following reaction equation: wherein Hal represents halogen, one of P1and P2is halogen and the other is Z' represents a group Z other than hydrogen, and the definitions of the other substituents Q1, Q2, X1, X2, R1, R2, R3, Y, and Z are as described in any one of claims 1-3; Preferably, the reaction (1) is carried out in the presence of a base, a catalyst, and a solvent; more preferably, the base is selected from at least one of an inorganic base or an organic base; the catalyst is selected from at least one of Pd(dppf)Cl2, Pd(dppf)Cl2·CH2Cl2, Pd(OAc)2, PdCl2, Pd(PPh3)4, or PdCl2(PPh3)2; and / or the solvent is an organic solvent or a mixture thereof with water, the organic solvent being dioxane, toluene, DMF, or DMSO; Preferably, the reactions (2) and (3) are carried out in the presence of a base and a solvent; more preferably, the base is selected from at least one of inorganic base or organic base; and / or the solvent is selected from at least one of aromatic hydrocarbon, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane, toluene or ethyl acetate.

5. A herbicidal composition, characterized by comprising: The herbicidal composition comprises at least one of the pyrimidine-substituted benzoxazinone compounds of any one of claims 1-3 in a herbicidally effective amount; preferably, further comprising formulation adjuvants; more preferably, further comprising other active ingredients.

6. A method for controlling weeds, comprising applying on plants or on weed areas a herbicidally effective amount of at least one of the pyrimidine-substituted benzoxazinone compounds of any one of claims 1-3 or the herbicide composition of claim 5.

7. Use of the pyrimidine-substituted benzoxazinone compounds of any one of claims 1-3 or the composition of claim 5 for controlling weeds, preferably, the pyrimidine-substituted benzoxazinone compounds are used for controlling weeds in transgenic crops or crops treated by genome editing technology.

8. An intermediate, as shown in formula II or IV of claim 4.

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