Substituted pyrazole compound, and preparation method therefor, herbicidal composition and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a substituted pyrazole compound, and a preparation method therefor, a herbicidal composition and the use thereof. The compound is as shown in general formula (I), wherein M1 and M2 each independently represent N or CR9, and at least one of M1 and M2 is N; M3 represents N or CR5; X represents hydrogen, halogen, -OX1, -(CO)OX2, -(CO)SX2 or -(CO)N(X2)2; X1 represents hydrogen, alkyl, alkenyl, alkynyl, etc.; X2 each independently represents hydrogen, alkyl, alkenyl, alkynyl, etc.; Z represents halogen, cyano, nitro, etc.; and Y, R1, R2, R3, R4, R5, R6, R7, R8, and R9 each independently represent hydrogen, halogen, cyano, etc. The compound has excellent herbicidal activity and crop safety.

Description

Substituted pyrazole 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 substituted pyrazole 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 herbicidal performance of these known compounds on harmful plants and the selectivity on 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 other issues, 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 substituted pyrazole compound, a preparation method thereof, a herbicidal composition and application, and the compound has excellent herbicidal activity and crop safety.

[0004] The technical solutions adopted by the present application are as follows:

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

[0006] M1, M2 respectively and independently represent N or CR9, and at least one of M1, M2 is N (for example, M1 is N, M2 is CR9; M1 is CR9, M2 is N; M1 is N, M2 is N);

[0007] M3 represents N or CR5;

[0008] X represents hydrogen, halogen, -OX1, -(CO)OX2, -(CO)SX2 or -(CO)N(X2)2;

[0009] X1 represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, -(CO)R 11 or -(CO)OR 11 , the alkyl, alkenyl or alkynyl is optionally substituted by at least one group selected from halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2;

[0010] X2represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclyl, said alkyl, alkenyl or alkynyl being optionally substituted with at least one group selected from halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2;

[0011] Z represents halogen, cyano, nitro, alkenyl, alkynyl, alkyl, alkenyl or alkynyl substituted with at least one group selected from halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2;

[0012] Y, R1, R2, R3, R4, R5, R6, R7, R8, R9represent independently for each occurrence hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2, said alkyl, alkenyl or alkynyl being optionally substituted with at least one group selected from halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2;

[0013] n is 0, 1 or 2;

[0014] R 11 represent independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, said alkyl, alkenyl or alkynyl being optionally substituted with at least one group selected from halogen or alkoxy;

[0015] 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 10 , -SR 10 , -(CO)R 10 , -(CO)OR 10 , -(CO)N(R 10 )2, -(CS)N(R 10 )2, -(SO)R 10 or -(SO2)R 10 ; or two adjacent carbon atoms of the ring form a fused ring with -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH- which is unsubstituted or substituted with halogen; or one saturated carbon atom of the ring is linked to both ends of -OCH2CH2O- which is unsubstituted or substituted with halogen to form a ring structure;

[0016] R 10 are each independently hydrogen, alkyl, haloalkyl, aryl or heterocyclyl which is unsubstituted or substituted with at least one group selected from halogen, alkyl;

[0017] and the following compounds are excluded:

[0018] In one embodiment, X1represents hydrogen, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, aryl, heterocyclyl, -(CO)R 11 or -(CO)OR 11 , said C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl being optionally substituted with at least one group selected from halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2;

[0019] X2are each independently hydrogen, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, aryl or heterocyclyl, said C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl being optionally substituted with at least one group selected from halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R11 )2, which is optionally substituted by at least one group selected from halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR

[0020] Z represents halogen, cyano, nitro, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2, C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2, which is optionally substituted by at least one group selected from halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2;

[0021] Y, R1, R2, R3, R4, R5, R6, R7, R8, R9 independently represent hydrogen, halogen, cyano, nitro, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2, which is optionally substituted by at least one group selected from halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2;

[0022] R 11 independently represent hydrogen, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkylC1-C8alkyl, aryl, arylC1-C8alkyl, heterocyclyl or heterocyclylC1-C8alkyl, which C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl is optionally substituted by at least one group selected from halogen or C1-C8alkoxy;

[0023] 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, haloC1-C8alkyl, haloC2-C8alkenyl, haloC2-C8alkynyl, -OR 10 , -SR 10 , -(CO)R 10 , -(CO)OR 10 , -(CO)N(R 10 )2, -(CS)N(R 10 )2, -(SO)R 10 or -(SO2)R 10 ; or two adjacent carbon atoms in the ring form a fused ring with -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH- which is unsubstituted or substituted with halogen; or one saturated carbon atom in the ring is linked to both ends of -OCH2CH2O- which is unsubstituted or substituted with halogen to form a ring structure;

[0024] R 10 are each independently hydrogen, C1-C8alkyl, haloC1-C8alkyl, aryl or heterocyclyl which is unsubstituted or substituted with at least one group selected from halogen, C1-C8alkyl.

[0025] In another embodiment, X1represents hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, aryl, heterocyclyl, -(CO)R 11 or -(CO)OR 11 , said C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl being optionally substituted with at least one group selected from halogen, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2.

[0026] X2are each independently hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, aryl or heterocyclyl, said C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl being optionally substituted with at least one group selected from halogen, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2.

[0027] Z represents halogen, cyano, nitro, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2, C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl optionally substituted with at least one group selected from halogen, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2;

[0028] Y, R1, R2, R3, R4, R5, R6, R7, R8, R9 independently represent hydrogen, halogen, cyano, nitro, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2, said C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl being optionally substituted with at least one group selected from halogen, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2;

[0029] R 11 independently represent hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkylC1-C6alkyl, aryl, arylC1-C6alkyl, heterocyclyl or heterocyclylC1-C6alkyl, said C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl being optionally substituted with at least one group selected from halogen or C1-C6alkoxy;

[0030] The foregoing "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 10 , -SR 10 , -(CO)R 10 , -(CO)OR 10 , -(CO)N(R 10 )2, -(CS)N(R 10 )2, -(SO)R 10 , or -(SO2)R 10 ; or two adjacent carbon atoms in the ring form a fused ring with -OCH2O-, -CH2CH2CH2O-, or -CH=CHCH=CH- which is unsubstituted or substituted with halogen; or one saturated carbon atom in the ring is attached to both ends of -OCH2CH2O- which is unsubstituted or substituted with halogen to form a ring structure;

[0031] R 10 are each independently hydrogen, C1-C6alkyl, halogenated C1-C6alkyl, aryl or heterocyclyl which is unsubstituted or substituted with at least one group selected from halogen, C1-C6alkyl.

[0032] 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.

[0033] Unless otherwise specifically indicated, the term "aryl" as used herein includes, but is not limited to, phenyl, naphthyl, The term "heterocyclyl" as used herein includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups The term "heterocyclyl" as used herein includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups

[0034] The term "optionally" or "optional" means that the subsequently described event or circumstance can or can not occur, and thus that description encompasses 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 to mean that the group is substituted with one or more groups, which are the same or different, selected from those mentioned. In addition, the same or different substituents contained in the same or different substituents are each independently selected, which can be the same or different. This also applies to ring systems formed from different atoms and units. 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.

[0035] 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 attachment position can be attached at any position, including the position attached to C or N; if it is substituted, the substituents can also be substituted at any position, as long as the rules of chemical bond connection are met. For example, a heteroaryl group substituted with 1 methyl group may represent , etc.

[0036] If various functional groups are present, the present application also includes any keto and enol tautomeric forms and mixtures and salts thereof.

[0037] Stereoisomers can be obtained from mixtures obtained in the preparation by optical resolution. Stereoisomers can also be selectively prepared by using stereoselective reactions and using optically active starting materials and / or auxiliaries. For optical resolution, it is generally possible to use conventional methods (see Textbooks of Stereochemistry), for example the following methods for resolving mixtures into diastereomers, for example physical methods such as crystallization, chromatography, in particular column chromatography and high-pressure liquid chromatography, distillation methods, if appropriate under reduced pressure, extraction and other methods, usually with chromatographic separation on chiral stationary phases, which make it possible to separate residual mixtures of enantiomers. Suitable for preparative amounts or for industrial scale are methods such as, for example, 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.

[0038] The preparation method of the substituted pyrazole compound comprises the following steps:

[0039] When X represents -(CO)OX2, -(CO)SX2or -(CO)N(X2)2, the compound of formula II is reacted with the compound of formula III to obtain the compound of formula I', and the reaction equation is as follows:

[0040] When X represents halogen or -OX1, the compound of formula IV is reacted with the compound of formula III to obtain the compound of formula I", and the reaction equation is as follows: Then the target compound is obtained through a conventional substitution reaction.

[0041] When X is hydrogen, it can be obtained from the compound of formula I' through a conventional hydrolytic decarboxylation reaction, or from the compound of formula I" through a conventional reduction reaction.

[0042] wherein L represents halogen, and the definitions of substituents M1, M2, M3, X, R1, R2, R3, R4, R6, R7, R8, Y and Z are as described above.

[0043] In one embodiment, the reaction for preparing the compound of formula I' or I" is carried out in the presence of a base and a solvent.

[0044] In another embodiment, the base is at least one selected from inorganic bases (such as NaOH, KOH, KF, NaH or KH, etc.) or organic bases (such as n-butyllithium, t-butyllithium, sodium t-butoxide, potassium t-butoxide, etc.).

[0045] In another embodiment, the solvent is at least one selected from toluene, dichloroethane, dimethyl sulfoxide, acetonitrile, ethyl acetate, diethyl ether, hexane or tetrahydrofuran.

[0046] In addition, the compound of the present application can be prepared according to the method shown in WO2023099354A, etc.

[0047] A herbicidal composition comprising a herbicidally effective amount of at least one of the substituted pyrazole compounds; preferably further comprising a formulation aid; more preferably further comprising other active ingredients.

[0048] A method for controlling weeds, comprising applying a herbicidally effective amount of at least one of the substituted pyrazole compounds or the herbicidal composition to plants or weed areas.

[0049] Use of at least one of the substituted pyrazole compounds or the herbicidal composition in controlling weeds, preferably, the substituted pyrazole compounds are used to prevent weeds in useful crops, which are genetically modified crops or crops treated by genome editing technology.​

[0050] An intermediate, as described by Formula II.

[0051] An intermediate, as described by Formula IV.

[0052] The compounds of the present application have outstanding herbicidal activity against a number of economically important monocotyledonous and dicotyledonous harmful plants. The active substances of the present application are also effective against perennial weeds which grow from rhizomes, rootstocks or other perennial organs and are difficult to control. In this connection, it is generally immaterial whether the substances are used before sowing, before or after germination. Particular mention can be made of the examples of monocotyledonous and dicotyledonous weed groups 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, Echinochloa, Digitaria, Cynodon and Cyperus, and the perennials of the genera Agropyron, Cynodon, Imperata and Sorghum, and the perennial Cyperus.

[0053] As regards 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, for example Echinochloa, Sagittaria, Alisma, Alocasia and Cyperus, under the uncertain conditions of rice sowing. 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 when the weeds have emerged with cotyledons, and finally the weeds can die completely 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, V. persica, Viola tricolor and Amaranthus, Galium and Kochia.

[0054] Although the compounds of the present application have outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not harmful or are only negligibly harmful to important economic crop plants, for example wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. In particular, there is a very good compatibility with cereal crops, for example wheat, barley and maize, in particular wheat. The compounds of the present application are therefore very suitable for the selective control of unwanted plants in crop plants or ornamental plants.

[0055] Due to their herbicidal properties, these active substances can be used for controlling harmful plants in genetically engineered plants which are known or will be developed in the future. Genetically engineered plants usually have superior properties, for example resistance to certain pesticides, particularly to certain herbicides, resistance to plant diseases or to the causative microorganisms of plant diseases, for example to certain insects or fungi, bacteria or viruses. Other special properties are associated with the following properties of the products, for example quantity, quality, storage stability, components and special ingredients. Thus, genetically engineered plant products are known which have an increased starch content or an improved starch quality or a different fatty acid composition.

[0056] The compounds of the formula I or their salts according to the application are preferably used in the cultivation of economically important genetically engineered crops and ornamental plants, for example cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or in the cultivation of sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, 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 the action of herbicides or which have been rendered resistant to the action of herbicides by genetic engineering.

[0057] Traditional methods for 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-0221044 A, EP-0131624 A). For example, several methods have been described:

[0058] - for improving starch synthesis in plants, crop plants are modified by genetic engineering (for example WO 92 / 11376, WO 92 / 14827, WO 91 / 19806);

[0059] - genetically engineered crop plants which are resistant to certain herbicides, for example to herbicides of the class of glufosinate herbicides (for example EP-0242236 A, EP-0242246 A) or to herbicides of the class of glyphosate herbicides (WO 92 / 00377) or to herbicides of the class of sulfonylurea herbicides (EP-0257993 A, US-5013659 A);

[0060] - genetically engineered crop plants of, for example, cotton, which are capable of producing toxins of Bacillus thuringiensis (Bt toxins) which protect the plants from the attack of certain pests (EP-0142924 A, EP-0193259 A);

[0061] - genetically engineered crop plants which have an improved fatty acid composition (WO 91 / 13972).

[0062] A number of molecular biological techniques are known which make it possible to produce transgenic plants with improved properties (see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, New York; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd Edition 1996 or Christou, Trends in Plant Science 1 (1996) 423-431)). In order to achieve the genetic engineering operations, 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.

[0063] It is possible to produce plant cells with reduced activity of a gene product, for example by expressing at least one suitable antisense-RNA, sense-RNA to achieve the effect of co-suppression, or by expressing at least one suitably constructed ribozyme which specifically cleaves the transcript of the gene product in question.

[0064] 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, these parts having to be sufficiently long to achieve the effect of antisense 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.

[0065] 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 the DNA sequence to ensure localization in a particular location. These sequences are known to the person skilled in the art (see, 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).

[0066] Using known techniques, it is possible to recombine the transgenic plant cells into whole plants. The transgenic plants can be any desired plant species, i.e. monocotyledonous and dicotyledonous plants. In this way, it is possible to obtain transgenic plants with improved properties by overexpression, inhibition or suppression of homologous (= natural) genes or gene sequences, or by expression of heterologous (= foreign) genes or gene sequences.

[0067] When using the active substances according to the application 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, the spectrum of weed control can be improved or enlarged, the application rate at the time of application can be improved, the combination of the preferred transgenic crop's resistance and the herbicide's performance is very good, and the growth and yield of the transgenic crop plant is influenced. The use of the compounds according to the application as herbicides for controlling harmful plants in transgenic crop plants is therefore also provided.

[0068] In addition, the compounds according to the application can significantly regulate the growth of crop plants. By regulating the components involved in plant metabolism, the use of these compounds allows targeted control of the plant and promotes harvesting, for example, by drying and dwarfing the growth of the plant. Furthermore, they are suitable for regulating and inhibiting the growth of undesired plants without destroying the growth of the crop. Inhibition of the growth of the plant plays a very important role in many monocotyledonous and dicotyledonous crops, since it can reduce or completely prevent lodging.

[0069] The compounds according to the application can be applied using the usual formulations, using wettable powders, emulsifiable concentrates, sprayable solutions, powders or granules. The application therefore also provides herbicidal compositions comprising the compounds of the formula I. The compounds of the formula I can be formulated in various ways depending on the usual biological and / or chemical-physical parameters. Suitable examples of formulation types are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions, for example oil-in-water and water-in-oil (EW), 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 spreading and soil application, injection granules, coating granules and absorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (ultra-low-volume) formulations, microencapsulations and wax formulations. These individual formulation types are known and are described, for example, in Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], 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.

[0070] Necessary formulation aids, such as inert substances, surface-active agents, solvents and other additives, are likewise known and are described, for example, in Watkins' "Pesticide Formulation [Oxirane adduct surfactants], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Kϋchler "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th edition 1986.

[0071] Wettable powders are capable of being dispersed in water to give homogeneous suspensions, and comprise in addition to the active substance, diluents or inert substances, ionic and non-ionic surfactants (wetting agents, dispersing agents), for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethyl fatty amines, fatty alcohol polyglycol ether sulphates, alkyl sulphonates, alkylphenyl sulphonates, sodium lignosulphonate, sodium 2,2'-dinaphthylmethane-6,6'-disulphonate, sodium dibutylnaphthalene sulphonate or sodium oleylmethyltauride. To prepare wettable powders, the herbicidal active substance is finely ground, for example using conventional apparatus such as hammer mills, fan mills and jet mills, and the adjuvants are mixed in simultaneously or in sequence.

[0072] Concentrated emulsions are prepared by dissolving the active substance in an organic solvent, for example 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.

[0073] ​The active substances and finely divided solid substances, such as talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth, are ground to a powder. Suspensions based on water or oil can be prepared by wet grinding, for example, using a commercially available pearl mill, with or without the addition of a surfactant of the other formulation type as described above.

[0074] Emulsions, for example oil-in-water emulsions (EW), can be prepared using aqueous organic solvents, using stirrers, colloid mills and / or static mixers, if desired, with the addition of a surfactant of the other formulation type as described above.

[0075] Granules are prepared by spraying the active substance onto adsorptive substances, using inert material granules, or by concentrating the active substance onto the surface of a carrier, for example sand, kaolin, and granulating the inert material by means of a binder, for example polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated using the methods used for the preparation of granules for fertilizers, if desired, with admixture of fertilizers. Water-soluble granules are prepared using the usual methods, for example spray-drying, fluidized-bed granulation, pan granulation, mixing using a high-speed mixer and extrusion without solid inert material.

[0076] For the preparation of granules using pan, fluidized-bed, extruder and spray-coating methods, reference is made to the processes described, for example, in the "Handbook of Spray Drying", 3rd edition 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration", Chemical and Engineering, 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook", 5th edition, 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", 5th edition, Blackwell Scientific Publications, Oxford 1968, pages 101-103.

[0077] Agricultural chemical formulations usually contain from 0.1 to 99 %, in particular from 0.1 to 95 %, by weight, of active substance of the formula I. The concentration of active substance in wettable powders is, for example, from about 10 to 99 %, the usual formulation components making up the remainder to 100 % by weight. The concentration of 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 active substance, whereas sprayable solutions contain from about 0.05 to 80 %, preferably from 2 to 50 %, by weight, of active substance. The content of active substance in water-suspension granules is, for example, between 1 and 95 %, preferably between 10 and 80 %, by weight, depending on whether the active substance is liquid or solid and on the auxiliaries, fillers, etc. used during granulation. The content of active substance in water-suspension granules is, for example, between 1 and 95 %, preferably between 10 and 80 %, by weight.

[0078] The formulations mentioned 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.

[0079] On the basis of these formulations, it is also possible to mix with other pesticidal active substances, such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and / or plant growth regulators, either as premixes or as tank mixes.

[0080] In tank mix or in tank mix formulations, suitable active substances which can be mixed with the active substances according to the application are, for example, the known substances from "The Pesticide Manual", 15thEdn, 2010, The British Crop Protection Council, London, and the literature cited therein. For example, the following herbicidal active substances mentioned below can be mixed with the mixtures of formula I: acetochlor, alachlor, butachlor, propisochlor, prodiamine, S- prodiamine, propachlor, dimethachlor, clacyfos, dichlorprop, dichlorprop-P, fenoxaprop-P, fluazifop-P, haloxyfop-P, propaquizafop, quizalofop-P, quizalofop-P- t-butyl, quizalofop-P- t-propyl, allidochlor, R- allidochlor, propanil, mefenacet, diphenamid, dimethenamid, dimethenamid-P, dichlormate, dichlormate-P, dimethenamid-P, flufenacet, mefenacet, metamifop, monalide, monalide-P, monalide-P- t-butyl, monalide-P- t-propyl, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamid-P, dimethenamidSapro- 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-Ametridione, Amibuzin, bromobenzonitrile, octanoyl bromobenzonitrile, octanoyl iodobenzonitrile, iodobenzonitrile, diphenylacetonitrile, bispyribac-sodium, hydroxybispyribac-sodium, Iodobonil, pyrimisulfuron-methyl, diflubenzuron, penoxsulam, sulfadiazine, chlorpyrifos-sulfuron-methyl, dichlorvos-sulfuron-methyl, fluroxypyr, bispyribac-sodium, pyrimisulfuron-methyl, pyrimisulfuron-methyl, pyrimisulfuron-methyl, bispyribac-sodium, nicosulfuron-methyl, sulfadiazine, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxazolidinone, isoxazolidinone, Fenoxasulfone, Me thiozolin, isopropalazine, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, bensulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, flumetsulam, pyrazosulfuron, pyrazosulfuron, flumethrin, mesotrione, pyrazosulfuron, flupropalazine, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, flupropalazine, pyrazosulfuron, flupropalazine, pyrazosulfuron, flupropalazine, pyrazosulfuron, flumezin, pentachlorophenol (sodium), terliphenol, terliphenol, terliphenol, pentonitrophenol, dinitrophenol, chlorpyrifos, terlisulfuron, terlisulfuron, terlisulfuron, terlisulfuron, terlisulfuron, terlisulfuron, terlisulfuron, terlisulfuron Flupyrazosulfuron, methyl methacrylate, tetrazolium methoxysulfuron, flupyrazosulfuron, chlorpyrifos, bromochlor, dimethoate, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, bentazon, pyrazosulfuron, oxadiazon, pyrazosulfuron, isoxadiazon, cyclohexane, isopropyl methoxysulfuron, propyl methoxysulfuron, indicarb, sodium chlorate, cogongrass Trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, forage fastener, bromophenol oxime, triazole sulfonate, methomyl, furazolidone, furazolidone, ethoxysulfuron, pyrimethanil, chlorphthalic acid, flurfluthrin, barnyardgrass, acrolein, bensulfuron-methyl, metribuzin, oat ester, thiamethoxam, styracil, hydroxyzine, methoxybenzone, pyrimethanil, chlorpyrifos, trichloropropionic acid, Alora c. Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, methylsulfuron, Cambendichlor, Cyproterinic acid, Thiamethoxam, Etnipromidone, Etnipromidone, Etnipromidone-methyl ...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. ,

[0081] When used, commercially available formulations are diluted in a common manner if necessary, such as with water for wettable powders, concentrated emulsions, suspensions, and granules suspended in water. Powders, granules for soil application, or solutions for broadcasting and spraying generally do not require further dilution with an inert substance before use. The required dosage of Formula I compound varies with external conditions, such as temperature, humidity, and the nature of the herbicide used. It can vary considerably, for example, from 0.001 to 1.0 kg ai / ha, or more active ingredient, but is preferably between 0.005 and 750 g ai / ha, particularly between 0.005 and 250 g ai / ha. Detailed Implementation

[0082] The following examples are for illustrative purposes only and should not be construed as limiting the invention in any way. The scope of protection of this invention is defined by the claims. Given the economy and diversity of the compounds, we have preferably synthesized several compounds, some of which are listed in Table 1 below. Specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustration of the invention and do not limit it. Those skilled in the art should not interpret this as limiting the scope of the invention to the following compounds.

[0083] Table 1. Compound structures and their properties 1 H NMR values

[0084] Several methods for preparing the compounds of the present application are illustrated in the following Schemes and Examples. Starting materials can be purchased from commercial suppliers or prepared by known literature methods or as otherwise described herein. 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 following Schemes, other starting materials and conditions can readily be substituted. Modifications of the synthetic routes described below can be made and will be apparent to those skilled in the art, and such modifications are included within the scope of the present application. Further, the synthetic methods described below can be further modified in light of the disclosure herein, using conventional chemistry known to those of ordinary skill in the art. For example, appropriate groups can be protected during the course of the reaction, and the like.

[0085] The following method examples are provided to further illustrate the preparation of the compounds of the present application, and the specific materials, amounts and conditions are not intended to limit the scope of the application. The reagents used in the synthesis of the compounds described below can be purchased from commercial suppliers or readily prepared by one of ordinary skill in the art.

[0086] Representative compounds are prepared as follows, and other compounds are prepared in a similar manner.

[0087] 1. Synthesis of compound 5

[0088] (1) Compound 5-1 (12.0 g, 1.00 mmol) was dissolved in THF in a three-necked flask, and replaced with nitrogen. LDA (32.1 mL, 1.50 mmol) was added at -78 °C under stirring. After stirring for 0.5 h, a solution of DMF (4.69 g, 1.50 mmol) in THF was added. After the addition was completed, the reaction was allowed to proceed for 0.5 h. The reaction was quenched by adding saturated ammonium chloride solution. The reaction mixture was extracted with ethyl acetate and water. The aqueous phase was extracted with ethyl acetate once more. The combined organic phase was dried and concentrated. Silica gel column chromatography gave intermediate 5-2 (9.00 g, 68%) as a light yellow oil.

[0089] (2) 2-bromo-5-chloro-3-fluoropyridine (400 mg, 1.91 mmol) was dissolved in toluene (8.00 mL), replaced with nitrogen for three times, reduced to -78 °C with dry ice / ethyl acetate, added n-butyllithium (2.5 M, 0.78 mL, 1.94 mmol), maintained the temperature for 15 min, added compound 5-2 (500 mg, 1.62 mmol) to the system, maintained the temperature for 45 min. LCMS monitored the reaction complete. The reaction was restored to room temperature, the reaction was concentrated, diluted with ethyl acetate, the organic phase was washed with water and saturated brine, dried and concentrated, the residue was purified by column chromatography (EA / PE = 1 / 10) to obtain brown oil 5 (500 mg, 70%).

[0090] 2. Synthesis of compound 91

[0091] Compound 91-1 (0.5 g, 1.37 mmol) was dissolved in 20 ml DMSO, added compound 91-2 (0.32 g, 1.5 mmol) and potassium tert-butoxide (0.53 g, 6.83 mmol), after adding, stirred at room temperature overnight. LCMS monitored the reaction complete. The reaction was poured into ice water, extracted with ethyl acetate, the organic phase was washed with water and saturated brine, dried and concentrated, the residue was purified by column chromatography (EA / PE = 1 / 3) to obtain compound 91 (0.4 g, 53.7%).

[0092] 3. Synthesis of compound 92

[0093] Compound 91 (0.3 g, 0.55 mmol) was dissolved in 20 ml anhydrous ethanol, added hydrochloric acid (0.2 g, 5.5 mmol) dropwise, after adding, stirred at 80 °C overnight. LCMS monitored the reaction complete, concentrated, the residue was purified by column chromatography (EA / PE = 1 / 4) to obtain compound 92 (0.18 g, 69.1%).

[0094] Biological activity evaluation:

[0095] The activity level criteria for plant destruction (i.e. growth control rate) are as follows:

[0096] 9: complete death;

[0097] 8: growth control rate greater than or equal to 90% and less than 100%;

[0098] 7: growth control rate greater than or equal to 80% and less than 90%;

[0099] 6: growth control rate greater than or equal to 70% and less than 80%;

[0100] 5: growth control rate is greater than or equal to 50% and less than 70%;

[0101] 4: growth control rate is greater than or equal to 30% and less than 50%;

[0102] 3: growth control rate is greater than or equal to 20% and less than 30%;

[0103] 2: growth control rate is greater than or equal to 10% and less than 20%;

[0104] 1: growth control rate is less than 10%;

[0105] 0: no effect.

[0106] The above growth control rate is fresh weight control rate.

[0107] Post-emergence test experiment:

[0108] The seeds of monocotyledonous and dicotyledonous weeds and the seeds of main crops are placed in plastic pots with soil, and then covered with 0.5-2 cm soil, and the test plants are treated at 2-3 leaf stage after 2 weeks of sowing, the test compounds of the present application are dissolved in acetone, then Tween 80 is added, 1.5 liters / ha of methyl oleate emulsion is used as synergist, and a certain concentration of solution is diluted with water, and sprayed on the plants by a spray tower. After 3 weeks of culture in the greenhouse after application, the experimental results of weeds are counted, and the representative data are shown in Table 2.

[0109] Table 2 Post-emergence test experiment results Note: N represents no data.

[0110] Pre-emergence test experiment:

[0111] The seeds of monocotyledonous and dicotyledonous weeds and the seeds of main crops are placed in plastic pots with soil, and then covered with 0.5-2 cm soil, and the test compounds of the present application are dissolved in acetone, then Tween 80 is added, and a certain concentration of solution is diluted with water, and sprayed immediately after sowing. After 4 weeks of culture in the greenhouse after application, the experimental results are observed, and the representative data are shown in Table 3.

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

[0113] At the same time, through many tests, it is found 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.

[0114] Finally, it should be noted that the above examples are merely used to illustrate the technical solutions of the present application but not to limit the present application. Although the present application 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 application can be modified or equivalent replaced without departing from the spirit and scope of the technical solutions of the present application.

Claims

1. A substituted pyrazole compound of the formula I: ###0001### or a salt thereof. wherein, M1, M2 independently represent N or CR9, and at least one of M1, M2 is N; M3 represents N or CR5; X represents hydrogen, halogen, -OX1, -(CO)OX2, -(CO)SX2 or -(CO)N(X2)2; X1represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, -(CO)R 11 or -(CO)OR 11 , said alkyl, alkenyl or alkynyl being optionally substituted by at least one radical chosen from halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; X2represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclyl, said alkyl, alkenyl or alkynyl being optionally substituted with at least one member selected from the group consisting of halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; Z represents halogen, cyano, nitro, alkenyl, alkynyl, alkyl, alkenyl or alkynyl substituted with at least one group selected from halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2; Y, R1, R2, R3, R4, R5, R6, R7, R8, R9 represent, independently from each other, hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2, said alkyl, alkenyl or alkynyl being optionally substituted by at least one group selected from halogen, cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; n is 0, 1 or 2; R 11 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl, or heterocyclylalkyl, said alkyl, alkenyl, or alkynyl being optionally substituted with at least one group selected from halo or alkoxy; The foregoing "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 10 , -SR 10 , -(CO)R 10 , -(CO)OR 10 , -(CO)N(R 10 )2, -(CS)N(R 10 )2, -(SO)R 10 , or -(SO2)R 10 ; or two adjacent carbon atoms of the ring form a fused ring with -OCH2O-, -CH2CH2CH2O-, or -CH=CHCH=CH- which is unsubstituted or substituted with halogen; or one saturated carbon atom of the ring is attached to both ends of -OCH2CH2O- which is unsubstituted or substituted with halogen to form a ring structure; R 10 are independently of each other hydrogen, alkyl, haloalkyl, aryl or heterocyclyl, which are unsubstituted or substituted by at least one group selected from the group consisting of halogen, alkyl; and the following compounds are excluded:

2. The substituted pyrazole compound according to claim 1, wherein X1represents hydrogen, Ci-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C8-cycloalkyl, aryl, heterocyclyl, -(CO)R 11 or -(CO)OR 11 , said Ci-C8-alkyl, C2-C8-alkenyl or C2-C8-alkynyl being optionally substituted with at least one radical selected from halogen, C3-C8-cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; X2represents independently for each occurrence hydrogen, Ci-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, aryl or heterocyclyl, said Ci-C8alkyl, C2-C8alkenyl or C2-C8alkynyl being optionally substituted with at least one radical selected from the group consisting of halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; Z represents halogen, cyano, nitro, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2, C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl substituted with at least one group selected from halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2; Y, R1, R2, R3, R4, R5, R6, R7, R8, R9 represent, independently from each other, hydrogen, halogen, cyano, nitro, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2, said C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl being optionally substituted by at least one radical chosen from halogen, C3-C8cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; R 11 each independently represents hydrogen, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkylC1-C8alkyl, aryl, arylC1-C8alkyl, heterocyclyl or heterocyclylC1-C8alkyl, said C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl being optionally substituted by at least one group selected from halogen or C1-C8alkoxy; The foregoing "C3-C8cycloalkyl", "heterocyclyl" or "aryl" is optionally substituted with at least one radical selected from the group consisting of oxo, halogen, cyano, nitro, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, haloC1-C8alkyl, haloC2-C8alkenyl, haloC2-C8alkynyl, -OR 10 , -SR 10 , -(CO)R 10 , -(CO)OR 10 , -(CO)N(R 10 )2, -(CS)N(R 10 )2, -(SO)R 10 , or -(SO2)R 10 ; or two adjacent carbon atoms of the ring form a fused ring with -OCH2O-, -CH2CH2CH2O-, or -CH=CHCH=CH- which is unsubstituted or substituted with halogen; or one saturated carbon atom of the ring is attached to both ends of -OCH2CH2O- which is unsubstituted or substituted with halogen to form a ring structure; R 10 are independently from each other and within each group independently from each other hydrogen, C1-C8-alkyl, halo-C1-C8-alkyl, aryl or heterocyclyl, which is unsubstituted or substituted by at least one group selected from the group consisting of halogen, C1-C8-alkyl.

3. The substituted pyrazole compound according to claim 1, wherein X1represents hydrogen, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, aryl, heterocyclyl, -(CO)R 11 or -(CO)OR 11 , said Ci-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl being optionally substituted with at least one radical selected from halogen, C3-C6-cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; X2represents independently for each occurrence hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, aryl, or heterocyclyl, said C1-C6alkyl, C2-C6alkenyl, or C2-C6alkynyl is optionally substituted with at least one member from the group consisting of halogen, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 , or -N(R 11 )2; Z represents halogen, cyano, nitro, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2, C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl substituted with at least one group selected from halogen, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2; Y, R1, R2, R3, R4, R5, R6, R7, R8, R9, independently represent hydrogen, halogen, cyano, nitro, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)R 11 , -(CO)OR 11 , -(CO)N(R 11 )2, -S(O) n R 11 or -N(R 11 )2, said C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl being optionally substituted by at least one radical chosen from halogen, C3-C6cycloalkyl, aryl, heterocyclyl, -OR 11 , -(CO)OR 11 , -S(O) n R 11 or -N(R 11 )2; R 11 each independently represents hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkylC1-C6alkyl, aryl, arylC1-C6alkyl, heterocyclyl or heterocyclylC1-C6alkyl, said C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl being optionally substituted by at least one group selected from halogen or C1-C6alkoxy; The foregoing "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, haloC1-C6alkyl, haloC2-C6alkenyl, haloC2-C6alkynyl, -OR 10 , -SR 10 , -(CO)R 10 , -(CO)OR 10 , -(CO)N(R 10 )2, -(CS)N(R 10 )2, -(SO)R 10 , or -(SO2)R 10 ; or two adjacent carbon atoms of the ring form a fused ring with -OCH2O-, -CH2CH2CH2O-, or -CH=CHCH=CH- which is unsubstituted or substituted with halogen; or one saturated carbon atom of the ring is attached to both ends of -OCH2CH2O- which is unsubstituted or substituted with halogen to form a ring structure; R 10 are independently from each other and within each group independently from each other hydrogen, C1-C6-alkyl, halo-C1-C6-alkyl, aryl or heterocyclyl, which is unsubstituted or substituted by at least one group selected from the group consisting of halogen, C1-C6-alkyl; Preferably, the compound is selected from any one of Table 1 in the specification.

4. A method for preparing the substituted pyrazole compound according to any one of claims 1-3, comprising the following steps: When X represents -(CO)OX2, -(CO)SX2, or -(CO)N(X2)2, a compound represented by the general formula II is reacted with a compound represented by the general formula III to produce a compound represented by the general formula I', as shown in the following reaction equation: When X represents halogen or -OX1, the compound of general formula IV to react with a compound of the general formula III to obtain a compound of the general formula I" then the target compound is prepared through a conventional substitution reaction; when X is hydrogen, the compound is prepared from a compound as shown in Formula I' through a conventional hydrolytic decarboxylation reaction, or from a compound as shown in Formula I" through a conventional reduction reaction; wherein L represents halogen, and the definitions of M1, M2, M3, X, R1, R2, R3, R4, R6, R7, R8, Y and Z are as described in any one of claims 1-3; Preferably, the reaction for preparing the compound of Formula I' or I" 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 or an organic base, and the solvent is selected from at least one of toluene, dichloroethane, dimethyl sulfoxide, acetonitrile, ethyl acetate, diethyl ether, hexane or tetrahydrofuran.

5. A herbicidal composition, characterized by comprising: comprising at least one of the substituted pyrazole compounds according to any one of claims 1-3 in a herbicidally effective amount; preferably, further comprising a formulation auxiliary; more preferably, further comprising other effective ingredients.

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

7. Use of the substituted pyrazole compound according to any one of claims 1-3 or the composition according to claim 5 for controlling weeds, preferably, the substituted pyrazole compound is used for controlling weeds in useful crops, and the useful crops are genetically modified 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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