Pyrrolidone herbicide

Abstract

The invention discloses a compound shown as a formula I, a stereoisomer or a salt thereof, and # imgabs0, wherein R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl and halogenated C1-C6 alkyl respectively, and R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl and halogenated C1-C6 alkyl; r is a halogenated C1-C6 alkyl group or a halogenated C3-C6 cycloalkyl group. The compound disclosed by the invention has a relatively good weeding effect and a relatively wide application prospect.

Description

Technical Field

[0001] The present invention belongs to the field of pesticides, and specifically relates to a novel pyrrolidone compound, their nitrogen oxides, stereoisomers, isotope derivatives and salts thereof, and a herbicidal composition containing the novel pyrrolidine compound, their nitrogen oxides, stereoisomers, isotope derivatives and salts thereof. Background Art

[0002] Achieving efficient and selective control of weed growth in crops or cash crops is a long-standing goal of selective weed control, for example, in the following crops, rice, soybeans, sugar beets, corn, potatoes, wheat, barley, tomatoes and plantation crops, but not limited thereto. If weed growth in crops is not effectively controlled, it will cause a significant reduction in yield. Similarly, it is also important to control undesirable vegetation (weeds) in non-cultivated areas.

[0003] Pyrrolidone herbicides are disclosed in CN106414403A and CN107709310A. Among them, tetrafluthrin is disclosed in China CN106414403A (ZL201480074726.8). According to the novel mechanism of action and excellent product performance of tetrafluthrin, its annual peak sales are expected to reach US$300 million to US$400 million.

[0004] Tetflupyrolimet, chemical name: (3S, 4S)-2′-fluoro-1-methyl-2-oxo-4-[3-(trifluoromethyl)phenyl]pyrrolidine-3-carboxanilide; CAS registration number: 2053901-33-8; molecular formula: C19H16F4N2O2; its chemical structure is as follows:

[0005]

[0006] The research and development direction in the herbicide field is to continue to study new high-performance herbicide compounds that are more effective, more economical, less toxic, safer to the environment, or have different sites of action. Summary of the invention

[0007] The invention obtains a compound with excellent herbicidal effect by selecting a specific substituent on the nitrogen atom of pyrrolidone in the prior art for herbicidal use.

[0008] Specifically, the present invention discloses a compound of formula I (including all stereoisomers), including its N-oxide and its salt, agricultural compositions containing them, and their use as herbicides:

[0009]

[0010] in,

[0011] R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl;

[0012] R is a halogenated C1-C6 alkyl group or a halogenated C3-C6 cycloalkyl group.

[0013] The present invention also discloses a pesticide composition, which comprises a herbicidally effective amount of the compound of formula I of the present invention, N-oxide or salt and a pesticide adjuvant, wherein the pesticide adjuvant is at least one selected from a surfactant, a solid diluent or a liquid diluent.

[0014] The above pesticide composition of the present invention optionally further comprises at least one herbicide selected from other herbicides.

[0015] The above pesticide composition of the present invention optionally further comprises at least one selected from other herbicides and herbicide safeners.

[0016] The present invention also discloses a method for controlling the growth of undesirable vegetation, which comprises contacting the vegetation or its environment with a herbicidally effective amount of a compound of formula I, an N-oxide, a salt or a composition of the present invention. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise explicitly stated, in the entire specification and claims.

[0018] As used herein, the terms "comprising," "including," "comprising," "including," "having," "containing," "containing," "characterized by," or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any expressly specified limitation. For example, a composition, mixture, process, or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, or method.

[0019] The phrase "consisting of" in this invention excludes any unrecited element, step, or ingredient. If in a claim, such a phrase will render the claim closed-ended so that it does not include materials other than those recited, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim, rather than immediately preceding it, it is limited only to the elements mentioned in that clause; other elements are not excluded from the claim as a whole.

[0020] In the present invention, "essentially consisting of..." is used to define a composition or method that includes materials, steps, features, components, or elements other than those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the subject matter. The term "essentially consisting of..." is intermediate between "comprising" and "consisting of..."

[0021] Where terms such as "comprising" define subject matter in the present invention, it should be understood that (unless otherwise indicated) the specification should be interpreted as also describing such subject matter using the terms "consisting essentially of" or "consisting of."

[0022] In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, condition A or B is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0023] As used herein, the term "broadleaf" used alone or in conjunction with a phrase such as "broadleaf weeds" refers to dicots or dicots, a term used to describe a class of angiosperms characterized by a plumule having two cotyledons.

[0024] Where the compounds according to the invention are capable of existing in tautomeric forms, the description of the compounds above and below is to be understood as also comprising the corresponding tautomeric forms, where applicable, even if these are not explicitly mentioned in each case.

[0025] If the compounds of the formula I described herein have one or more chiral centers and therefore exist as enantiomers or diastereomers, the pure enantiomers, racemates or diastereomers can be used in the compositions of the invention.

[0026] Any asymmetric atom (eg, carbon, etc.) in the compounds disclosed herein may exist in a racemic or enantiomerically enriched form, such as the (R)-, (S)- or (R,S)-configuration.

[0027] If the compounds of formula I of the present invention have functional groups that can be ionized, they can also be used in the form of their agricultural salts or mixtures thereof. The salts of the present invention can be inorganic salts such as hydrochlorides, hydrobromides, sulfates, nitrates, phosphates, but are not limited thereto. And organic acid salts such as formates, acetates, oxalates, fumarates, methanesulfonates, benzenesulfonates, but are not limited thereto.

[0028] Unless otherwise specified, all technical terms used in the present disclosure have the same meaning as commonly understood by those skilled in the art to which the present disclosure belongs. All patents and publications related to the present disclosure are incorporated herein by reference in their entirety.

[0029] The term "alkyl" as used in the present disclosure means a saturated straight or branched monovalent hydrocarbon group. When the number of carbon atoms is not used when describing an "alkyl", it means that the alkyl has any number of carbon atoms. When the number of carbon atoms is used when describing an "alkyl", it means that the alkyl has the stated number of carbon atoms. For example, an alkyl group can be C1-C 20 Alkyl refers to a saturated, straight-chain or branched, monovalent hydrocarbon group containing 1 to 20 carbon atoms, wherein the alkyl group may be optionally substituted with one or more substituents described in the present disclosure. Unless otherwise specified, the alkyl group contains 1 to 20 carbon atoms. In some embodiments, the alkyl group contains 1 to 12 carbon atoms, such as "C1-C 12 In some other embodiments, the alkyl group is an alkyl group containing 1-6 (1, 2, 3, 4, 5 or 6) carbon atoms, i.e., a "C1-C6 alkyl"; in some other embodiments, the alkyl group is an alkyl group containing 1-4 (1, 2, 3 or 4) carbon atoms, i.e., a "C1-C4 alkyl"; in some other embodiments, the alkyl group contains 1-3 carbon atoms, i.e., a "C1-C3 alkyl".

[0030] Examples of alkyl groups include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), n-propyl (n-Pr, -CH2CH2CH3), isopropyl (i-Pr, -CH(CH3)2), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -CH(CH3)CH2CH3), u, -C(CH3)3), n-pentyl (-CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1 -butyl (-CH2CH(CH3)CH2CH3), n-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3 ), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3), n-heptyl, n-octyl, and the like.

[0031] The term "halogenated alkyl" refers to, for example, a linear or branched alkoxyalkyl group substituted by one or more halogen atoms which may be the same or different from each other. For example, the halogenated C1-C6 alkyl group refers to a linear or branched alkyl group having 1 to 6 carbon atoms substituted by one or more halogen atoms which may be the same or different from each other, for example, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, 2,2-difluoroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2,2-trichloroethyl, 2,2,2-tribromoethyl, 1,3-difluoro-2-propyl, 1,3-dichloro-2-propyl, 1-chloro-3-fluoro -2-propyl, 1,1,1-trifluoro-2-propyl, 2,3,3,3-tetrafluoro-n-propyl, 1,1,1,3,3,3-hexafluoro-2-propyl, 1,1,1,3,3,3-hexafluoro-2-chloro-2-propyl, 1,1,1,3,3,3-hexafluoro-2-bromo-2-propyl, 1,1,2,3,3,3-hexafluoro-2-chloro-n-propyl, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propyl, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propyl, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propyl, 2,2,3,3,3-pentafluoro-n-propyl, 3-fluoro-n-propyl, 3-chloro-n-propyl, 3-bromo-n-propyl, nonafluoro-n-butyl, nonafluoro-isobutyl, nonafluoro-sec-butyl, or nonafluoro-tert-butyl, and the like, but are not limited thereto.

[0032] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0033] The halogenated C3~C6 cycloalkyl group of the present invention refers to a monocyclic saturated hydrocarbon with 3 to 6 ring members substituted by halogen, and the C3~C6 cycloalkyl group is such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of the halogenated C3~C6 cycloalkyl group include 2-fluorocyclopropyl, 3-fluorocyclobutyl, 2,2-difluorocyclopropyl or 3,3-difluorocyclobutyl, etc., but are not limited thereto.

[0034] The "salt" of the present disclosure includes acid addition salts and base addition salts, and suitable bases are hydroxides, carbonates, bicarbonates of alkali metals and alkaline earth metals, especially sodium, potassium, magnesium, and calcium salts, and ammonium. The salt can be a salt added with an inorganic acid, and the inorganic acid can be hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid, or a salt added with an organic acid, and the organic acid can be formic acid, carbonic acid, and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

[0035] The leaving group of the present invention is usually a group that is easy to leave, such as halogen (such as fluorine, chlorine, bromine or iodine), p-toluenesulfonyl, methylsulfonyl, etc., but is not limited thereto.

[0036] Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires a lone pair of electrons to oxidize to an oxide, and those skilled in the art will also know which nitrogen-containing heterocycles can form N-oxides. Those skilled in the art will also know that tertiary amines can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art, and include oxidation of heterocycles and tertiary amines with peroxyacids such as peracetic acid and meta-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for preparing N-oxides have been extensively described and reviewed in the literature.

[0037] Specifically, the present invention first discloses a compound of formula I, a stereoisomer thereof or a salt thereof,

[0038]

[0039] in,

[0040] R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl;

[0041] R is a halogenated C1-C6 alkyl group or a halogenated C3-C6 cycloalkyl group.

[0042] Preferably, in technical solution 1, R1, R2, R3, R4, R5, R6, R7, and R8 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl, and halogenated C1-C6 alkyl; preferably H, halogen, cyano, hydroxyl, methyl, ethyl, propyl, or trifluoromethyl;

[0043] Preferably in technical solution 2, R is a halogenated C1-C6 alkyl, preferably FCH2-.

[0044] Preferably, in technical solution 3, R is a halogenated C3-C6 cycloalkyl group, preferably a halogenated C3-C4 cycloalkyl group, and particularly preferably a 2,2-difluorocyclopropyl group or a 3,3-difluorocyclobutyl group.

[0045] The preferred compounds of the present invention are shown in Table 1:

[0046]

[0047] Table 1 Preferred compounds of the present invention

[0048]

[0049]

[0050] Particularly preferred compounds of the present invention are:

[0051]

[0052] The compound of the general formula I of the present invention can be synthesized from intermediate compound A and intermediate compound B, and the synthesis route is as follows:

[0053]

[0054] Wherein, R1, R2, R3, R4, R5, R6, R7, R8 and R are as defined above.

[0055] The compound A and B are prepared in the presence of lithium bis(trimethylsilyl)amide to obtain the compound of formula I.

[0056] Among them, the intermediate compound A can be synthesized by conventional technical means in the art, for example, by referring to the method disclosed in CN106414403A.

[0057] The intermediate compound A of the present invention,

[0058]

[0059] R1, R2, R3 and R4 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, preferably H;

[0060] R is a halogenated C1-C6 alkyl group or a halogenated C3-C6 cycloalkyl group, preferably one of FCH2-, 2,2-difluorocyclopropyl or 3,3-difluorocyclobutyl.

[0061] The herbicidal effective amount of the compounds disclosed in the present invention is determined by many factors. These factors include: the selected formulation, the method of application, the amount and type of vegetation present, growth conditions, etc. Generally speaking, the herbicidal effective amount of the compounds disclosed herein is from about 0.005 to about 20 kg / ha. In certain embodiments, the range is from about 0.01 to about 1 kg / ha. Those skilled in the art can easily determine the herbicidal effective amount required for the desired weed control level.

[0062] The compounds disclosed herein may also be mixed with one or more other biologically active compounds or agents, including herbicides, herbicide safeners, fungicides, insecticides, nematicides, bactericides, miticides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or insect pathogenic bacteria, viruses or fungi to form multi-component pesticides, thereby conferring even broader spectrum agricultural protection.

[0063] The mixture of the compounds of this invention and other herbicides can expand the activity spectrum of resisting additional weed species, and suppress the proliferation of any resistant biological type. Therefore, the present disclosure also relates to a composition comprising a compound of formula I (in a herbicidally effective amount) and at least one biologically active compound or reagent (in a biologically effective amount), and the composition may further include a pesticide adjuvant, such as, at least one of a surfactant, a solid diluent or a liquid diluent. Other active compounds or reagents can be formulated into a composition comprising at least one of a surfactant, a solid or a liquid diluent.

[0064] For the mixtures of the present disclosure, one or more other active compounds or agents may be formulated together with the compounds of Formula I of the present invention to form a premix, or one or more other biologically active compounds or agents may be formulated separately from the compounds of Formula I and the formulations combined together (e.g., in a spray tank) prior to administration, or alternatively, applied sequentially.

[0065] The herbicide that forms a mixture with the compound of formula I disclosed in the present invention can be selected from one or more of the following herbicide compounds, acetochlor, trifluorfen and its sodium salt, bensulfuron, acrolein (2-propenal), alachlor, fenthion, ametryn, amitriptyline, amidosulfuron, cyproconazole and its esters (such as methyl, ethyl) and salts (such as sodium, potassium), chlorpyrifos, cyproconazole, sulfamethoxam, ammonium sulfamate, thiabendazole, sulfamethoxam, atrazine, tetrazosulfuron, flubutyric acid, fenthion, fenthion ethyl, bencarbazone, fluazifop, furazolidone, benzylsulfuron, dithiocarb, bentazone, bicyclon, pyraclostrobin, flupyralid, pyraclostrobin, pyraclostrobin, bifenthion, bispyribac-butyl and its sodium salt, herbicide, bromobutyric acid, bromophenoxime, bromoxynil, bromoxynil octanoate, butachlor, fluorine Propylene glycol, chlorpyrifos, butachlor ... Clodinafop-butyl, clomazone, barnyardgrass, clopyralid, clopyralid ethanolamine, clorac-sulfuron, benzylpyruvate, cyanazine, cyclopyrimorate, cyprosulfuron, cyfluthrin, 2,4-D and its butoxy, butyl, isooctyl and isopropyl esters and their dimethylammonium salts, diethanolamine salts and triethanolamine salts, cypermethrin, dalapon, dalapon sodium, dazomethane, 2,4-DB and its dimethylammonium salt, potassium salt and sodium salt, betaine, dichlorvos, dicamba and its diethylene glycol ammonium salt, dimethylammonium salt, potassium salt and sodium salt, dichlorvos nitrile, dipropionic acid, diclofenac, dicloso, difenac dimethyl sulfate, fluazifop, flufenpyr, oxazolidinone, piperidine, dimethoate, isopentanol, dimethenamid, dimethenamid-P, thiamethoxam, dimethoate and its sodium salt, dimethoate, terbutal, dimethoate, diquat, fluthiopyr, diuron, DNOC, fenthiocarb, EPTC, pentocarb, ethylbutene, ethametsulfuron, Ethimethoate, ethidium bromide, fluazifop-butyl, ethoxysulfuron, ethosulfuron, oxadiazine, fenoxaprop-butyl, isoxadiazine, fenquinotrione, tetrazolam, fenoxaprop-TCA, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl , fluazifop-butyl and its sodium salt, fluazifop-butyl ... imazethapyr, imazethapyr ammonium, pyraclostrobin, indole, triazine indole, iodosulfuron, methyl iodosulfuron, ioxynil, ioxynil octanoate, ioxynil sodium, triazolam, isoproturon, isoxamethoxam, isoxamethoxam, isoxamethoxazole, isoxamethoxazole, lactofen, lenacil, liuron, bud-inhibiting agent, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl ester, MCPA-butoxyethyl ester) and thioesters (e.g., MCPA-ethylthioester), MCPB,

[0066] and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), 2-methyl-4-chloropropionic acid, 2-methyl-4-chloropropionic acid, benzathine, sulfamethoxam, mesosulfuron, mesotrione, sodium metabisulfuron, metamifenamid, metamethoxam, pyraclostrobin, methylbenthiazide, arsenic acid and its calcium salts, monoammonium, monosodium and disodium salts, methylthiazide, methoxybenthiazide, bromothiazide, isopropylamine, isopropylamine, sulfamethoxam, sulfamethoxam, methicillin, methicillin, methicillin, chloranil, naphthamide, naphthamide, naphthamide-M, naphthamide, chloranil, nicosulfuron, dafosulfuron, pyraclostrobin, pyraclostrobin, amoxicillin, propargyl oxadiazine, oxadiazine, oxadiazine, oxadiazine, oxadiazine, ethoxyflurane Ether, paraquat dichloride, chloranil, nonanoic acid, pendimethalin, penoxsulam, meclofenamide, cyclopentadione, fluazifop, pethoxyamid, pethoxyamid, pyrazoline, pyrazoline potassium, fluazifop, pinoxaden, pyrazophos, pretilachlor, primisulfuron, aminopropyrin, cyproconazole, promethazine, promethazine, promethazine, propamid, propamid, propamid, propamid, propamid, propamidoxam, propamidoxam, propamidoxam, propamidoxam, promethazine, promethazine, propamidoxam, propamidoxam, propamidoxam, propamidoxam, propamidoxam, promethazine, promethazine, propamidoxam, propamidoxam, propamidoxam, propamidoxam, promethazine, promethazine, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline, pyrazoline , pyrimthiocarb, pyrimthiocarb sodium, rock-sulphate sulfone, methoxysulfone, dichloroquine, clomiphene, quinac, quinac, quinalkonium, quizalofop-p-ethyl, quizalofop-p-ethyl, sulfonesulfuron, bensulfuron, sethoxydim, cypermethrin, simazine, cypermethrin, sulfotrione, sulfotrione, sulfotrione, 2,3,6-TBA, TCA, TCA-sodium, oxadiazine, terbuthiazine, terfurotrione, cypermethrin, demecarb, terbuthiazine, terbuthiazine, terbuthiazine, methoxysulfone, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, tiafenacil, cypermethrin, pyraclostrobin, oxadiazine, wild wheat, fluazifop-butyl, etherbensulfuron, triazifop-butyl, bensulfuron, triclopyr, triclopyr-triethylammonium, chlorpyrifos Cyclopentanone, thiocarbamide, trifloxysulfuron, fluralin, flufensulfuron, trifloxysulfuron, cypermethrin, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridine-2(1H-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexene-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazine-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole, 3-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]dihydro-1,5-dimethyl-6-thioxo-1,3,5-triazine-2,4(1H,3H)-dione, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1- cyclohexene-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-picolinic acid methyl ester, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide.

[0067] In the above compositions, the weight ratio of the compound of formula I of the present invention to other herbicides is generally between about 1:3000 and about 3000: 1. Of note is a weight ratio between about 1:300 and about 300: 1 (e.g., a ratio between about 1:30 and about 30: 1).

[0068] Those skilled in the art can readily determine by simple experimentation the biologically effective amount of the active ingredient necessary for the desired spectrum of biological activity. It will be apparent that the inclusion of these additional components can expand the spectrum of weeds controlled beyond that controlled by the compounds of Formula 1 alone.

[0069] In some cases, the combination of the compounds of the present invention with other active ingredients (particularly herbicidal) compounds can result in greater than additive (i.e. synergistic) effects on weeds and / or less than additive (i.e. safening) effects on crops or other desired plants. It has always been desirable to reduce the amount of active ingredients released in the environment while ensuring effective pest control.

[0070] The above-mentioned composition can also be added with a detoxifying effective amount of a herbicide safener, which is a substance added to the herbicide formulation to eliminate or reduce the phytotoxic effects of the herbicide on certain crops. These compounds protect crops from herbicide damage, but usually cannot prevent herbicides from controlling unwanted vegetation. Examples of the herbicide safener include, but are not limited to, chlorpyrifos, chlorpyrifos-butyl, benzylpyrim, chlorpyrifos-butyl, cyproconazole, cyproconazole, dichlorpropamide, dicyclonon, dietholate, chlorpyrifos, chlorpyrifos, fluazifop, chlorpyrifos, fluazifop, chlorpyrifos, isoxadiazole, isoxadiazole, mephenate, chlorpyrifos, naphthalene dicarboxylic anhydride, chlorpyrifos, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N-(aminocarbonyl)-2-methylbenzenesulfonamide. )-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG191), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and -2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.

[0071] The antidote-effective amount of safener can be easily determined by those skilled in the art through simple experiments.

[0072] A method for controlling unwanted vegetation disclosed herein comprises applying a herbicidally effective amount of a compound of the present invention (e.g., as a composition described herein) to the locus of the vegetation. It should be noted that the embodiments related to the methods of use are those of the compounds of the above embodiments. Many of the compounds of the present invention are particularly useful for selectively controlling weeds in crops such as wheat, barley, corn, soybeans, sunflowers, cotton, rapeseed and rice, as well as specialty crops such as sugarcane, citrus, fruit and nut crops.

[0073] The following examples should be construed as merely illustrative and not limiting of the present disclosure in any way. The steps in the following examples illustrate the procedures for each step in the overall synthetic transformation, and the starting materials for each step are not necessarily prepared by specific preparative experiments whose procedures are described in other examples or steps. Percentages are by weight, except for chromatographic solvent mixtures or unless otherwise specified. Unless otherwise specified, the parts and percentages of chromatographic solvent mixtures are by volume.

[0074] 1) Preparation Example

[0075] Example 1: 1-(2,2-difluorocyclopropyl)methyl)-N-(2-fluorophenyl)-2-oxo-4-(3-(trifluoromethyl)phenyl)pyrrolidine-3-carboxamide (Compound 18)

[0076] Step 1: Synthesis of Intermediate 2

[0077]

[0078] Dissolve 2,2-difluorocyclopropanecarboxylic acid (5 g, 0.04 mmol) in tetrahydrofuran (70 ml), cool to 0°C, add lithium aluminum hydride (2.27 g, 0.06 mmol) in batches, continue stirring for 30 minutes, warm to room temperature, and stir for 4 hours. Cool in an ice-water bath, carefully drop water (6.5 ml), then drop 15% sodium hydroxide aqueous solution (3 ml), stir at room temperature for about 30 minutes, filter, and concentrate under reduced pressure (temperature is 30°C) to obtain a crude intermediate 2 (4 g) for later use.

[0079] Step 2: Synthesis of Intermediate 3

[0080]

[0081] Under argon protection, the intermediate 2 (4 g, crude product) was dissolved in dichloromethane (50 ml), N,N,N',N'-tetramethyl-1,6-hexanediamine (4.46 g, 0.026 mmol) was added, the temperature was lowered to 0°C, and p-toluenesulfonyl chloride (10.59 g, 0.056 mmol) was added in batches, and the mixture was stirred at room temperature for 4 h. A saturated aqueous sodium chloride solution (500 ml) was added, and the mixture was extracted with ethyl acetate, the organic phases were combined, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain the intermediate 3 (9.1 g).

[0082] Step 3: Synthesis of Intermediate 5

[0083]

[0084] Under argon protection, 3-trifluoromethylbenzaldehyde (10g, 0.057mmol) was dissolved in tetrahydrofuran (100ml), potassium tert-butoxide (7.1g, 0.063mmol) was added, the temperature was lowered to 10°C, stirred for 0.5h, and then triethyl phosphoacetate (12.9g, 0.057mmol) was slowly added dropwise, the temperature was raised to room temperature, and stirred for 1h. Saturated sodium chloride aqueous solution (1000ml) was added, and the mixture was extracted with ethyl acetate, the organic phases were combined, dried (sodium sulfate), filtered, and spin-dried to obtain a crude intermediate 5 (13.5g) for later use.

[0085] Step 4: Synthesis of intermediate 6

[0086]

[0087] Under argon protection, the intermediate 5 (13.5 g) was dissolved in nitromethane (50 ml), cooled to 0°C, and 1,8-diazobispiro[5.4.0]undec-7-ene (9.26 g, 0.061 mmol) was slowly added dropwise, and the mixture was stirred for 30 minutes, then warmed to room temperature and stirred for 1 hour. Saturated aqueous ammonium chloride solution (500 ml) was added, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried (sodium sulfate), filtered, and spin-dried to obtain a crude intermediate 6 (16.7 g) for later use.

[0088] Step 5: Synthesis of Intermediate 7

[0089]

[0090] Under argon protection, intermediate 6 (16.7 g) was dissolved in anhydrous ethanol (200 ml), nickel chloride hexahydrate (19.5 g, 0.082 mmol) was added, and sodium borohydride (6.2 g, 0.164 mmol) was slowly added in batches, and stirring was continued for 1 h. Saturated aqueous ammonium chloride solution (500 ml) was added dropwise, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried (sodium sulfate), filtered, and spin-dried to obtain a crude intermediate 7 (19.4 g) for later use.

[0091] Step 6: Synthesis of Intermediate 8

[0092]

[0093] Under argon protection, the intermediate 7 (19.4 g) was dissolved in anhydrous tetrahydrofuran (300 ml), cooled to 0°C, and sodium hydrogen sulfide (6.56 g, 0.27 mmol) was added in batches. After stirring for 30 minutes, the mixture was warmed to room temperature and stirred for 2 hours. A saturated aqueous ammonium chloride solution (500 ml) was added dropwise, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain the intermediate 8 (10 g).

[0094] Step 7: Synthesis of Intermediate 9

[0095]

[0096] Under argon protection, intermediate 8 (2g, 0.0087mmol) and intermediate 3 (2.74g, 0.0104mmol) were dissolved in N,N-dimethylformamide (30ml), cesium carbonate (5.69g, 0.017mmol) was added, and stirred for 2h. Water (100mL) was added, extracted with ethyl acetate, and the organic phases were combined. The organic phase was washed with saturated brine, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain intermediate 9 (1.8g).

[0097] Step 8: Synthesis of compound 18

[0098]

[0099] Under argon protection, intermediate 9 (1.8 g, 0.0056 mmol) was dissolved in anhydrous tetrahydrofuran (30 ml), cooled to -70 ° C, and lithium bis(trimethylsilyl)amide (11.2 mL, 0.011 mmol) was slowly added dropwise, and stirring continued for 30 minutes, and then 2-fluorophenyl isocyanate (1.15 g, 0.0084 mmol) was slowly added dropwise, and stirred for 2 h. Saturated aqueous ammonium chloride solution (50 ml) was added dropwise, extracted with ethyl acetate, the organic phases were combined, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain compound 18 (1.4 g).

[0100] 1 H NMR (400MHz, CDCl3) δ9.76 (d, J=14.4Hz, 1H), 8.32–8.12 (m, 1H), 7.64–7.46 (m, 4H) ,7.16–6.97(m,3H),4.23(q,J=8.8Hz,1H),4.10–4.01(m,1H),4.00–3.80(m,1H),3 .71–3.63(m,1H),3.52(ddd,J=56.0,10.1,7.9Hz,1H),3.08(ddd,J=13.5,8.2,5.0 Hz,1H),1.93–1.74(m,1H), δ1.66–1.56(m,1H).1.20(ddd,J=9.3,5.6,2.8Hz,1H).

[0101] Example 2: 1-((3,3-difluorocyclobutyl)methyl)-N-(2-fluorophenyl)-2-oxo-4-(3-(trifluoromethyl)phenyl)pyrrolidine-3-carboxamide (Compound 21)

[0102] Step 1: Synthesis of intermediate 11

[0103]

[0104] Dissolve 3,3-difluorocyclobutanecarboxylic acid (5 g, 0.036 mmol) in tetrahydrofuran (70 ml), cool to 0°C, add lithium aluminum hydride (2.03 g, 0.055 mmol) in batches, continue stirring for 30 minutes, warm to room temperature, and stir for 4 hours. Cool in an ice-water bath, carefully drop water (6 mL), then drop 15% sodium hydroxide aqueous solution (3 ml), stir at room temperature for about 30 minutes, filter, and concentrate under reduced pressure (temperature is 30°C) to obtain a crude intermediate 11 (5 g) for later use.

[0105] Step 2: Synthesis of intermediate 12

[0106]

[0107] Under argon protection, the intermediate 11 (5 g, crude product) was dissolved in dichloromethane (60 ml), N,N,N',N'-tetramethyl-1,6-hexanediamine (4.43 g, 0.026 mmol) was added, the temperature was lowered to 0°C, and p-toluenesulfonyl chloride (10.53 g, 0.055 mmol) was added in batches, and the mixture was stirred at room temperature for 4 h. A saturated aqueous sodium chloride solution (500 ml) was added, and the mixture was extracted with ethyl acetate, the organic phases were combined, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain the intermediate 12 (8.7 g).

[0108] Step 3: Synthesis of intermediate 13

[0109]

[0110] Under argon protection, intermediate 8 (2g, 0.0087mmol) and intermediate 12 (2.89g, 0.0104mmol) were dissolved in N,N-dimethylformamide (30ml), cesium carbonate (5.69g, 0.017mmol) was added, and stirred for 2h. Water (100mL) was added, extracted with ethyl acetate, and the organic phases were combined. The organic phase was washed with saturated brine, dried (sodium sulfate), filtered, and dried, and the residue was purified by silica gel column chromatography to obtain intermediate 13 (1.6g).

[0111] Step 4: Synthesis of compound 21

[0112]

[0113] Under argon protection, the intermediate 13 (1.6 g, 0.0048 mmol) was dissolved in anhydrous tetrahydrofuran (30 ml), cooled to -70 ° C, and lithium bis(trimethylsilyl)amide (9.6 mL, 0.010 mmol) was slowly added dropwise, and stirring continued for 30 minutes, and then 2-fluorophenyl isocyanate (0.98 g, 0.0072 mmol) was slowly added dropwise, and stirred for 2 h. Saturated aqueous ammonium chloride solution (50 ml) was added dropwise, and extracted with ethyl acetate, the organic phases were combined, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain compound 2 (1.1 g).

[0114] 1 H NMR (400MHz, CDCl3) δ9.78 (s, 1H), 8.24 (t, J = 7.6Hz, 1H), 7.61–7.50 (m, 4H), 7.15–

[0115] 7.04(m,3H),4.22(dd,J=17.0,8.5Hz,1H),3.85(t,J=9.5Hz,1H),3.68(d,J=8.8Hz,1H) ,3.63–3.55(m,2H),3.49–3.43(m,1H),2.75(dt,J=12.8,8.7Hz,2H),2.51–2.35(m,3H).

[0116] Example 3, 1-(2-fluoroethyl)-N-(2-fluorophenyl)-2-oxo-4-(3-(trifluoromethyl)phenyl)pyrrolidine-3-carboxamide (Compound 3)

[0117] Step 1: Synthesis of intermediate 15

[0118]

[0119] Under argon protection, 2-fluoroethanol (5g, 0.78mmol) was dissolved in dichloromethane (70ml), N,N,N',N'-tetramethyl-1,6-hexanediamine (9.4g, 0.055mmol) was added, the temperature was lowered to 0°C, and p-toluenesulfonyl chloride (22.34g, 0.117mmol) was added in batches, and the mixture was stirred at room temperature for 4h. Saturated sodium chloride aqueous solution (500ml) was added, and the mixture was extracted with ethyl acetate, the organic phases were combined, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain intermediate 12 (15g).

[0120] Step 2: Synthesis of intermediate 16

[0121]

[0122] Under argon protection, intermediate 8 (2g, 0.0087mmol) and intermediate 15 (2.29g, 0.0105mmol) were dissolved in N,N-dimethylformamide (30ml), cesium carbonate (5.69g, 0.017mmol) was added, and stirred for 2h. Water (100mL) was added, extracted with ethyl acetate, and the organic phases were combined. The organic phase was washed with saturated brine, dried (sodium sulfate), filtered, and dried, and the residue was purified by silica gel column chromatography to obtain intermediate 16 (1.5g).

[0123] Step 3: Synthesis of compound 3

[0124]

[0125] Under argon protection, intermediate 16 (1.5 g, 0.0055 mmol) was dissolved in anhydrous tetrahydrofuran (30 ml), cooled to -70 ° C, and lithium bis(trimethylsilyl)amide (11 mL, 0.011 mmol) was slowly added dropwise, and stirring continued for 30 minutes, and then 2-fluorophenyl isocyanate (1.12 g, 0.0082 mmol) was slowly added dropwise, and stirred for 2 h. Saturated aqueous ammonium chloride solution (50 ml) was added dropwise, extracted with ethyl acetate, the organic phases were combined, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain compound 3 (1.3 g).

[0126] 1 H NMR(400MHz, CDCl3)δ9.80(s,1H),8.24(dd,J=11.1,5.0Hz,1H),7.55(ddd,J=26.0,16.0,8.3Hz,4H),7.12–6.98(m,3H),4.77– 4.66(m,1H),4.65–4.53(m,1H),4.22(q,J=8.9Hz,1H),3.96(t,J=9.7Hz,1H),3.86–3.65(m,3H),3.62(dd,J=16.7,8.2Hz,1H).

[0127] 2. Bio-test Examples

[0128] 1) Determination of indoor herbicidal activity

[0129] 1. Preparation of medicine

[0130] After the original drug of the compounds 1-34 of the present invention and the reference compound tetrafluthrin was dissolved in acetone or DMF, a test solution of a required concentration was prepared with a 1‰ Tween 80 aqueous solution according to the test requirements.

[0131] 2. Target preparation and processing

[0132] Sow the grass weed barnyard grass in a paper cup with a diameter of 7 cm filled with nutrient soil, cover it with 1 cm of soil after sowing, suppress and water it, and then cultivate it in the greenhouse according to the conventional method. When the weeds reach the 2-3 leaf stage, spray the stems and leaves after seedlings, and observe the results after 20 days in the greenhouse.

[0133] 3. Evaluation method

[0134] The efficacy observation was carried out by visual inspection, and the standards were as follows

[0135] 0-same as control, drug-resistant, protection efficiency is less than 10%;

[0136] 1- Growth is slightly affected, slightly inhibited, poor activity, and the control effect is 10% to less than 30%;

[0137] 2- Growth is affected, slight bleaching, poor activity, and the control effect is 30% to less than 50%;

[0138] 3- Growth is affected, whitening is obvious, activity is moderate, and the control effect is 50% to less than 70%;

[0139] 4-More sensitive, significant bleaching, better activity, control efficiency is 70% to less than 90%;

[0140] 5-Extremely sensitive, completely bleached, basically dead, protection rate is 90% to 100%.

[0141] 4. Test results

[0142] When used at a dosage of 50 g ai / ha, the compounds 1-34 of the present invention and the control compound tetrafluthria-chlor achieved a control effect of more than level 3 on barnyard grass, among which the preferred compounds 3, 9-22, 24-34 achieved a control effect of more than level 4, and the particularly preferred compounds 3, 18, and 21 achieved a control effect of more than level 5.

[0143] When used at a dosage of 25 g ai / ha, the compounds 3, 9-22, 24-34 of the present invention have a level 4 control effect on barnyard grass. Preferably, the compounds 3, 18, and 21 of the present invention reach level 5, the compound 23 has a level 3 control effect on barnyard grass, and the compounds 1-2, 4-8 and the reference compound tetrafluthrin have a level 2 control effect on barnyard grass.

[0144] When the dosage is 5g ai / ha, the control effect of compounds 3, 9-22, 24-34 of the present invention on barnyard grass reaches above level 2, preferably the control effect of compound 18 reaches level 4, and compounds 3 and 21 reach level 3; the control effect of compound 23 on barnyard grass reaches level 1, and the control effect of compounds 1-2, 4-8 and the reference compound tetrafluthrin on barnyard grass is level 0.

[0145] II) Experimental effect of killing grass weeds in rice fields

[0146] 1. Materials and Methods

[0147] 1.1 Test reagents

[0148] Compound 3, Compound 18, Compound 21 and reference compound tetrafluthrin (TFBL)

[0149] 1.2 Test targets and crops

[0150] Target: Echinochloa crusgalli, Leptochloa chinensis

[0151] Crop: Rice

[0152] 1.3 Test methods

[0153] 1.3.1 Field trial of killing grass weeds in rice fields (Balingshan, Shashi District, Jingzhou City, Hubei Province, August 12, 2024)

[0154] The test site is located in Balingshan, Shashi District, Jingzhou City, Hubei Province, and the test crop is rice. The application period is 24h after sowing, and the rice field is sown after ploughing. The test agents compound 3, compound 18, and compound 21 are configured to a mass concentration of 10ppm. 5% TFBL is used as the control agent, configured to a mass concentration of 10ppm, and a clear water blank control is also set. The test treatment area is 8㎡, each treatment is repeated 4 times, and the random block group is arranged.

[0155] A Huayou brand electric backpack sprayer was used for conventional spraying. Surveys were conducted 7, 14, 30, and 45 days after application. The number of weeds after application was checked and recorded, and the control effect was calculated.

[0156] Calculation method of drug efficacy:

[0157] Control effect (%) = {(number of weeds in the control area - number of weeds in the treatment area) / number of weeds in the control area} × 1002 Results and analysis

[0158] Table 2 Results of field test on killing grass weeds in rice fields

[0159]

[0160] Note: The protective efficacy (%) in the table is the average value of each replicate.

Claims

1. A compound of formula I, a stereoisomer thereof or a salt thereof, in, R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl; R is a halogenated C1-C6 alkyl group or a halogenated C3-C6 cycloalkyl group.

2. The compound of formula I according to claim 1, its stereoisomer or its salt, characterized in that The R1, R2, R3, R4, R5, R6, R7, and R8 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl, and halogenated C1-C6 alkyl; preferably H, halogen, cyano, hydroxyl, methyl, ethyl, propyl, or trifluoromethyl.

3. The compound of formula I according to claim 1, its stereoisomer or its salt, characterized in that The R is a halogenated C1-C6 alkyl group, preferably a fluoromethyl group.

4. The compound of formula I according to claim 1, its stereoisomer or its salt, characterized in that The R is a halogenated C3-C6 cycloalkyl group, preferably a 2,2-difluorocyclopropyl group or a 3,3-difluorocyclobutyl group.

5. A compound, characterized in that Selected from the following compounds, 6. A herbicidal composition, characterized in that: The herbicidal composition contains the compound according to any one of claims 1 to 6 and a pesticide adjuvant.

7. The herbicide composition according to claim 6, further comprising at least one or more of the following herbicides: acetochlor, acifluorfen and its sodium salt, bensulfuron, acrolein (2-propenal), alachlor, fenthion, ametryn, amitriptyline, amidosulfuron, cyproconazole and its esters, aminopyralid, cyproconazole, ammonium sulfamate, cyproconazole, sulfamethoxam, atrazine, tetrazosulfuron, flubutyric acid, fenthion, fenthion ethyl, bencarbazone, fluazifop, furazolidone, benzylsulfuron, dimethoate, bentazon, bicyclam, pyraclostrobin, bispyribac-butyl, bispyribac-butyl and its sodium salt, bromobutyric acid, bromobutyric acid, bromophenoxime, bromoxynil, bromoxynil octanoate Ester, butachlor, fluazifop-butyl, chlorpyrifos, butachlor, butachlor, butachlor, benzophenone, carbamate, triadimefon, catechin, methoxyfenoxam, chlorfenapyr, chlorbromid, chlormethyldan, herbicide, chlorsulfuron, chlorotoluron, chlorpropamide, chlorsulfuron, dimethyl chlorthalate, cypermethrin, indolone, cyproconazole, chlorpyrifos, cyclobenzophenone, clethodim, cyclopyrimorate, clodinafop-butyl, isocyanate, barnyardgrass, clopyralid, clopyralid ethanolamine, clopyralid, benzylpyruvate, cyanazine, cyclopyrimorate, cyprosulfuron, cyfluthrin, 2,4-D and its butoxy esters, butyl esters, isooctyl esters and isopropyl esters and their dimethyl ammonium salts, Diethanolamine salt and triethanolamine salt, cypermethrin, cypermethrin sodium, dazomethane, 2,4-DB and its dimethyl ammonium salt, potassium salt and sodium salt, betaine, dichlorvos, dicamba and its diethylene glycol ammonium salt, dimethyl ammonium salt, potassium salt and sodium salt, dichlorvos nitrile, dipropionic acid, diclofenac, diclofenac, dimethoate, dimethoate dimethyl sulfate, fluazifop, fluazifop, oxazolidinone, piperidine, dimethoate, isopentanol, dimethoate, dimethoate-P, thiamethoxam, dimethoate and its sodium salt, dimethoate, telofenol, dimethoate, diquat, fluthiopyr, diuron, DNOC, fenthiocarb, EPTC, pentocarb, ethidium bromide, ethidium bromide, ethidium bromide, flurbiprofen, ethidium bromide, ethidium bromide, oxazolidinone, ethidium bromide, oxazolidinone, ethidium bromide Diclofenac, isoxadiazole, fenquinotrione, tetrazoline, fenthiazolin, fenthiazolin-TCA, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl and its sodium salt, fluazifop-butyl, fluorenol butyl, fluazifop- ...Clopyrasulfuron-methyl, flupyralid, flupyralid, hexazinone, imazapic, methoxyfen-2, methazapic, imazapic, imazapic, imazapic, imazapic, pyrasulfuron-methyl, indole, triazine indole, iodinesulfuron-methyl, iodosulfuron-methyl, ioboxynil, ioboxynil octanoate, ioboxynil sodium, triazolam, isoproturon, isoxazolidinone, isoxazolidinone, Isotrione, isoxathiapiprolin, lactofen, lenacil, linuron, bud-inhibiting carbendazim, 2-methyl-4-chloropropionic acid, 2-methyl-4-chloropropionic acid, benzathine, flusulfamide, mesosulfuron, mesotrione, sodium metabisulfite, metamifop, metamifop, pyraclostrobin, methylbenzene, arsenic acid and its calcium salt, monoammonium salt, monosodium salt and Disodium salt, methyl oxadiazon, methoxybenzamide, bromothiocarb, isopropyl metolachlor, s-isopropyl metolachlor, sulfamethoxazole, methoxythiocarb, metsulfuron, metsulfuron-methyl, grass, green sulfamethoxazole, naphthamide, naphthamide, naphthamide-M, naphthamide, grass, nicosulfuron, dafofu, pingcaodan, pyrimidine sulfamethoxazole, amoxicillin, propargyl oxadiazon, oxadiazon, oxadiazon, oxadiazon, oxyfluorfen, paraquat dichloride, gram, nonanoic acid, dipentadiazine, penfosulam, meclofenamide, cyclopentadiazine, fluazifop, pethoxyamid, bendichlor, picloram, picloram potassium, flupyralid, pinoxaden, piperafophos, pretilachlor, primisulfuron, aminopropane, cyclohexyl, cyproconazole, cyproconazole, cyproconazole, Propylene, diazinon, oxadiazine, propazine, bensulfuron, isopropylamine, propansulfuron, propazine sulfamethoxam, propansulfuron, pyrazogyl, pyrazol, pyrazosulfuron, pyrazogyl, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrazosulfuron, pyrimisulfan, pyrimisulfuron sodium, rockweed sulfone, methoxysulfone, quinclorac, clomiphene, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, sulfamethoxam, sulfamethoxam, sethoxydim, cypermethrin, simazine, simethoxazole, sulfosulfuron, sulfosulfuron, sulfosulfuron, terbuthiuron, terbuthiuron triketone, cyclosulfuron, demechlor, terbuthion, terbuthion, terbuthion, terbuthion, methoxyfenacet, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, tiafenacil, thiamethoxam, pyraclostrobin, oxamethoxam, wild wheat, fluazifop, ether bensulfuron, triazifop, bensulfuron, triclopyr, triclopyr-triethylammonium, chloranil, thiocarb, trifloxysulfuron, trifloxysulfuron, trifloxysulfuron, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridine-2(1H-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone,2-Chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole, 3-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]dihydro-1 ,5-dimethyl-6-thioxo-1,3,5-triazine-2,4(1H,3H)-dione, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-picolinic acid methyl ester, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide; Preferably, the weight ratio of the compound to other herbicides is generally between 1:3000 and 3000:1, more preferably between 1:300 and 300:1, most preferably between 1:30 and 30:

1.

8. The herbicide composition according to claim 7, characterized in that Add an effective amount of herbicide safener, wherein the herbicide safener is selected from one or more of the following compounds: fenthiocarb, fenthiocarb, benzylpyridin, fenthiocarb, cyproconazole, cyproconazole, dichlorvos, dicyclonon, dietholate, fenthiocarb, fenthiocarb, fenthiocarb, fluazifop, fenthiocarb, fluazifop, fenthiocarb, isoxadiazole, isoxadiazole, mephenate, deoxynivalenol, fenthiocarb ... Oxalone, naphthalene dicarboxylic anhydride, oxalonitrile, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone.

9. A method for controlling the growth of undesirable vegetation, the method comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound according to any one of claims 1 to 5 or a herbicide combination according to any one of claims 6 to 8.

10. Compound A, in, R1, R2, R3 and R4 are independently selected from H, halogen, cyano, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, preferably H; R is a halogenated C1-C6 alkyl group or a halogenated C3-C6 cycloalkyl group, preferably one of FCH2-, 2,2-difluorocyclopropyl or 3,3-difluorocyclobutyl.

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