How to control weeds

Abstract

The present invention relates to a method for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, comprising administering to the weeds, parts of the weeds, weed propagation material, or the locus of the weeds an effective amount of a compound represented by formula (I): [Formula 1] TIFF2025515962000011.tif42161 (wherein the substituents are as defined in claim 1), wherein the PPO-resistant weeds are weeds that are resistant to at least one PPO-inhibiting herbicide, except for the compound of formula (I).

Description

[Technical field]

[0001] The present invention relates to a method for controlling the growth of protoporphinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, comprising applying to the weeds, parts of the weeds, weed propagation material, or the locus of the weeds an effective amount of a compound of formula (I), where a PPO-resistant weed is a weed that is resistant to at least one PPO-inhibiting herbicide, except for the compound of formula (I). [Background technology]

[0002] Wang et al., Journal of Agricultural and Food Chemistry 2019 67(45), 12382-12392, disclose various N-isoxazolinylphenyltriazinones as promising protoporphyrinogen IX oxidase (PPO) inhibitors for use as herbicidal compounds. These and similar compounds are disclosed in WO 2016 / 095768 and WO 2020 / 063613.

[0003] Herbicide resistance has been known since the 1950s. Herbicide-resistant weeds, such as PPO inhibitor herbicide-resistant weeds, such as Acalypha spp., Amaranthus spp., Ambrosia spp., Avena spp., Conyza spp., Descurainia spp., Euphorbia spp. and Senecio spp., represent a serious problem for efficient weed control, since such resistant weeds are becoming more and more widespread and, when resistant weeds are present, application of the affected herbicide is much less effective than would normally be expected. In particular, PPO inhibitor herbicide-resistant weeds such as Amaranthus palmeri and Amaranthus tuberculatus are a major problem for farmers in many parts of the world. Moreover, the proportion of herbicide-resistant individuals increases over time due to selection pressures in situations where a single herbicide mode of action (MOA) family is repeatedly applied.

[0004] The primary mechanism of action of PPO inhibitor herbicides is the inhibition of protoporphyrinogen oxidase (PPO), an enzyme in chloroplast cells that oxidizes protoporphyrinogen IX (PPGIX) to produce protoporphyrin IX (PPIX). PPIX is important because it is a precursor molecule for both chlorophyll (necessary for photosynthesis) and heme (necessary for the electron transport chain). However, inhibitors of the PPO enzyme do not simply block the production of chlorophyll and heme. Inhibition of PPO by PPO inhibitors results in the accumulation of protoporphyrinogen IX, which leaks into the cytosol. Acting as a photosensitizer, the presence of protoporphyrinogen IX in the cytosol results in the formation of reactive oxygen species that attack and destroy lipid membranes resulting in cell death.

[0005] Many of the same mechanisms of resistance to PPO inhibitor herbicides have been found in different weed species, including the amino acid substitution R128M / G (also called R98) and the deletion of the codon (glycine) at position 210 (Δ210) in the PPX2 gene, which codes for the target enzyme of PPO inhibitor herbicides, i.e., PPO.

[0006] In crop protection it is desirable to increase the specificity and reliability of the action of active compounds, in particular it is desirable for crop protection products to simultaneously effectively control harmful weeds and be tolerated by useful plants. Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, there is a need for new methods of effectively controlling herbicide-resistant weeds, especially PPO inhibitor herbicide-resistant weeds, which at the same time are tolerated by useful plants and crops in the same field. [Means for solving the problem]

[0008] Surprisingly, it has been found that compounds of formula (I) provide effective control of PPO-resistant weeds.

[0009] According to a first aspect of the present invention, there is provided a method for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, comprising administering to the weeds, parts of the weeds, weed propagation material, or the locus of the weeds an effective amount of a compound of formula (I): [ka] (In the formula, Each R 1 and R 2 is selected from the group consisting of hydrogen and halogen; R 3 is hydrogen, C 1 ~C 4 Alkyl, CO 2 R 5 and C.H. 2 OR 6is selected from the group consisting of R 4 is hydrogen and C 1 ~C 4 is selected from the group consisting of alkyl, R 5 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Alkenyl, C 3 ~C 6 Alkynyl, C 1 ~C 4 Alkoxy C 1 ~C 4 Alkyl, C 1-4 Kalkyl carbonyl C 1-4 Alkyl and heterocyclyl C 1 ~C 3 is selected from the group consisting of alkyl, R 6 is C 1 ~C 2 Alkylsulfonyl, C 1 ~C 4 Alkylcarbonyl and C 3 ~C 4 cycloalkylcarbonyl; R 7 is hydrogen, C 1 ~C 4 Alkyl and C 1 ~C 4 haloalkyl; R 8 is hydrogen, amino, C 1 ~C 6 Alkyl, C 3 ~C 6 Alkenyl and C 3 ~C 6 alkynyl) applying a compound of The method is provided, wherein the PPO-resistant weed is a weed that is resistant to at least one PPO-inhibiting herbicide, except for the compound of formula (I). According to a second aspect of the present invention, an agrochemical composition is provided, comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically acceptable diluent or carrier. Such an agricultural composition may further comprise at least one additional active ingredient. In one embodiment, the additional active ingredient. Preferably, the additional active ingredient is S-metolachlor, glufosinate, L-glufosinate, glyphosate, mesotrione, bicyclopyrone or metribuzin.

[0010] According to a third aspect of the present invention, there is provided a method for controlling or preventing undesirable plant growth of weeds having a mutation at amino acid 128, amino acid 210, or amino acid 399 of a gene encoding a protoporphyrinogen oxidase enzyme, comprising applying a herbicidally effective amount of a compound of formula (I) or a composition comprising this compound as an active ingredient to the weeds, parts of weeds, weed propagation material, or locus of the weeds. Preferably, there is provided a method for controlling or preventing undesirable plant growth of weeds having a mutation at amino acid 128 and / or amino acid 210 of a gene encoding a protoporphyrinogen oxidase enzyme, comprising applying a herbicidally effective amount of a compound of formula (I) or a composition comprising this compound as an active ingredient to the weeds, parts of weeds, weed propagation material, or locus of the weeds.

[0011] According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds. In particular, there is provided the use of a compound of formula (I) for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, wherein the protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds have a mutation at amino acid 128, amino acid 210, and / or amino acid 399 of the gene encoding the protoporphyrinogen oxidase enzyme. Preferably, there is provided the use of a compound of formula (I) for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, wherein the protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds have a mutation at amino acid 128 and / or amino acid 210 of the gene encoding the protoporphyrinogen oxidase enzyme.

[0012] According to a fifth aspect of the present invention, there is provided the use of an agrochemical composition comprising a compound of formula (I) for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds. In particular, there is provided the use of a composition comprising a compound of formula (I) for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, the protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds having a mutation at amino acid 128, amino acid 210 and / or amino acid 399 of the gene encoding the protoporphyrinogen oxidase enzyme. Preferably, there is provided the use of a composition comprising a compound of formula (I) for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, the protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds having a mutation at amino acid 128 and / or amino acid 210 of the gene encoding the protoporphyrinogen oxidase enzyme. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The possible presence of one or more asymmetric carbon atoms in the compound of formula (I) means that the compound can be in chiral isomeric form, i.e., enantiomeric or diastereomeric form. Also, the restriction of rotation about a single bond can give rise to atropisomers. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof of the compound of formula (I). Similarly, formula (I) is intended to include all possible tautomers, if present, including lactam-lactim tautomers and keto-enol tautomers. The present invention includes all possible tautomeric forms of the compound of formula (I).

[0014] Similarly, when disubstituted alkenes are present, they may exist in the E or Z form or as a mixture of both in any ratio. The present invention includes all these possible isomeric forms and mixtures thereof for the compounds of formula (I).

[0015] The compounds of formula (I) are typically provided in the form of an agriculturally acceptable salt, a zwitterion, or a salt of an agriculturally acceptable zwitterion. The present invention encompasses all such agriculturally acceptable salts, zwitterions, and mixtures thereof in all proportions.

[0016] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).

[0017] As used herein, amino is —NH 2 means a group.

[0018] As used herein, "C 1 ~C 6 The term "alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. 1 ~C 4The term "alkyl" should be construed accordingly. 1 ~C 6 Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and its isomers such as iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl.

[0019] As used herein, "C 2 ~C 6 The term "alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond, having 2 to 6 carbon atoms, which may be in either the (E) or (Z) configuration, and attached to the remainder of the molecule by a single bond. 3 ~C 6 Alkenyl should be construed accordingly. 2 ~C 6 Examples of alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.

[0020] As used herein, "C 2 ~C 6 The term "alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having 2 to 6 carbon atoms and attached to the remainder of the molecule by a single bond. 3 ~C 6 The term "alkynyl" should be construed accordingly. 2 ~C 6 Examples of alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

[0021] As used herein, "C 1 ~C 6 The term "haloalkyl" refers to any of the C groups generally defined above substituted with one or more of the same or different halogen atoms.1 ~C 6 Refers to the alkyl radical. 1 ~C 4 Haloalkyl should be construed accordingly. 1- C 6 Examples of haloalkyl include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0022] As used herein, "C 1 ~C 4 Alkoxy C 1 ~C 4 The term "alkyl" refers to a group of the formula R b -OR a -, where R b is the C 1 ~C 4 is an alkyl radical, R a is the C 1-4 It is an alkylene radical.

[0023] As used herein, "C 1 ~C 4 Alkyl carbonyl C 1 ~C 4 The term "alkyl" refers to a group of the formula -R b C(O)R a In the formula, R a is the C 1 ~C 4 is alkyl, R b is the C 1-4 It is an alkylene radical.

[0024] As used herein, the term "heterocyclyl" or "heterocyclic" refers to a stable 5- or 6-membered non-aromatic monocyclic radical containing one, two, or three heteroatoms individually selected from nitrogen, oxygen, and sulfur. The heterocyclyl radical may be attached to the remainder of the molecule through a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dioxolanyl, morpholinyl, oxazinanyl, oxetanyl, or δ-lactamyl.

[0025] As used herein, "heterocyclyl C 1 ~C 2 The term "alkyl" refers to 1 ~C 2 It refers to a heterocyclic ring as defined above attached to the remainder of the molecule by an alkylene radical.

[0026] As used herein, "C 1-6 The term "alkylsulfonyl" refers to a group of the formula -S(O) 2 R a where R a is the C 1-6 It is an alkyl radical. 1-2 The term "alkylsulfonyl" should be construed accordingly.

[0027] As used herein, "C 1 ~C 4 The term "alkylcarbonyl" refers to a group of the formula R a C(O)- radical, where R a is the C 1 ~C 4 It is an alkyl radical.

[0028] As used herein, "C 3 ~C 8The term "cycloalkyl" refers to a stable monocyclic ring radical that is saturated and contains 3 to 8 carbon atoms. 3 ~C 8 Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0029] As used herein, "C 3 ~C 8 The term "cycloalkylcarbonyl" refers to a group of the formula R a C(O)- radical, where R a is C as defined above. 3 ~C 8 A cycloalkyl radical. C 3 ~C 4 Cycloalkylcarbonyl should be construed accordingly.

[0030] As used herein, the terms "PPO inhibitor herbicide resistant weeds", "PPO inhibitor herbicide resistant weeds", "PPO inhibitor resistant weeds", "PPO resistant weeds", "protoporphyrinogen IX oxidase inhibitor herbicide resistant weeds", "protoporphyrinogen IX oxidase inhibitor herbicide resistant weeds", "protoporphyrinogen oxidase inhibitor herbicide resistant weeds" and "protoporphyrinogen oxidase inhibitor herbicide resistant weeds" are synonymous and refer to, in relation to treatment with appropriate or over-appropriate rates of PPO inhibitor herbicide application, (1) Withstands treatment if it eradicates wild-type weeds; or (2) If it suppresses the growth of wild-type weeds, it exhibits significant vegetative growth or reproduction after treatment. Ability is inherited, developed, or acquired.

[0031] PPO-resistant weeds are weeds that are not controlled by application of known PPO inhibitor herbicides, other than the compounds of formula (I), whereas susceptible biotypes are controlled at the use rates.

[0032] Suitable agriculturally acceptable salts of the present invention may involve cations including, but not limited to, metals, conjugate acids of amines, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc.Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, Examples of suitable amines include amine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine.Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.

[0033] Suitable agriculturally acceptable salts of the present invention may involve cations including, but not limited to, metals, conjugate acids of amines, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc.Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, Examples of suitable amines include amine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine.Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.

[0034] The following list refers to compounds of formula (I) according to the invention and is intended to describe the substituent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 For any one of these substituents, any of the definitions given below may be combined with any other substituent definition given below or elsewhere in this document.

[0035] R 1 is selected from the group consisting of hydrogen and halogen. 1 is selected from the group consisting of hydrogen, chlorine and fluorine. More preferably, R 1 is selected from the group consisting of chlorine and fluorine.

[0036] R 2 is selected from the group consisting of hydrogen and halogen. 2 is selected from the group consisting of chlorine and bromine.

[0037] R 3 is hydrogen, C 1 ~C 4 Alkyl, CO 2 R 5 and C.H. 2 OR6 Preferably, R 3 CO 2 R 5 and C.H. 2 OR 6 More preferably, R 3 CO 2 R 5 It is.

[0038] R 4 is hydrogen and C 1 ~C 4 More preferably, R 4 is hydrogen and C 1 ~C 2 alkyl.

[0039] R 5 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Alkenyl, C 3 ~C 6 Alkynyl, C 1 ~C 4 Alkoxy C 1 ~C 4 Alkyl, C 1 ~C 4 Alkyl carbonyl C 1 ~C 4 Alkyl and Heterocyclyl C 1 ~C 3 Preferably, R is selected from the group consisting of alkyl. 5 H, CH 3 , C 2 H 5 , C.H. 3 CH 2 CH 2 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CH, (CH 3 ) 2 CHCH 2, (CH 3 ) 3 C, C.F. 3 CH 2 , allyl, propargyl, CH 3 OCH 2 CH 2 , C 2 H 5 OCH 2 CH 2 , C.H. 3 CO 2 CH 2 CH 2 and tetrahydrofuranmethyl. More preferably, R 5 is hydrogen, and C 1 ~C 4 alkyl.

[0040] R 6 is C 1 ~C 2 Alkylsulfonyl, C 1 ~C 4 Alkylcarbonyl and C 3 ~C 4 cycloalkylcarbonyl. Preferably, R 6 is C 1 ~C 2 Alkylsulfonyl, C 1 ~C 4 It is selected from the group consisting of alkylcarbonyl and cyclopropylcarbonyl.

[0041] R 7 is hydrogen, C 1 ~C 4 Alkyl and C 1 ~C 4 haloalkyl. Preferably, R 7 is C 1 ~C 4 More preferably, R is selected from the group consisting of haloalkyl. 7 CF 3 It is.

[0042] R 8 is hydrogen, amino, C 1 ~C 6Alkyl, C 3 ~C 6 Alkenyl and C 3 ~C 6 alkynyl. Preferably, R 8 is C 1 ~C 4 More preferably, R 8 CH 3 It is.

[0043] A preferred subset of compounds are R 1 is selected from the group consisting of hydrogen, chlorine and fluorine; R 2 is selected from the group consisting of chlorine and bromine, R 3 But CO 2 R 5 and C.H. 2 OR 6 R 4 But, H, CH 3 and C 2 H 5 R 5 But, H, CH 3 , C 2 H 5 , C.H. 3 CH 2 CH 2 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CH, (CH 3 ) 2 CHCH 2 , (CH 3 ) 3 C, C.F. 3 CH 2 , allyl, propargyl, CH 3 OCH 2 CH 2 , C 2 H 5 OCH 2 CH 2 , C.H. 3 CO 2 CH 2 CH 2 and tetrahydrofuranmethyl; R6 But, C 1 ~C 4 Alkylcarbonyl, cyclopropylcarbonyl and C 1 ~C 2 alkylsulfonyl; R 7 CF 3 and R 8 CH 3 It is, it is.

[0044] A more preferred subset of compounds is R 1 is selected from the group consisting of hydrogen, chlorine and fluorine; R 2 is selected from the group consisting of chlorine and bromine, R 3 CO 2 R 5 and R 4 But, H, CH 3 and C 2 H 5 R 5 But, H, CH 3 , C 2 H 5 , C.H. 3 CH 2 CH 2 , C.H. 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CH, (CH 3 ) 2 CHCH 2 , and (CH 3 ) 3 C; R 7 CF 3 and R 8 CH 3 It is, is.

[0045] An even more preferred subset of compounds are 1 is selected from hydrogen, chlorine and fluorine; R 2 is selected from chlorine and bromine, R 3 CO 2 R 5 and R 4 is methyl and R7 is trifluoromethyl, and R 8 Two particularly preferred compounds are those in which R 1 is selected from chlorine and fluorine, R 2 is chlorine and R 3 CO 2 R 5 and R 4 is methyl and R 7 is trifluoromethyl, and R 8 is methyl.

[0046] Most preferably, the compound of formula (I) is 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester (also referred to herein as “compound 8”).

[0047] Table of Examples This table is for R 7 is trifluoromethyl, and R 8 It discloses certain compounds of formula (I) where is methyl.

[0048] [Table 1]

[0049] A list of weeds that are resistant to inhibition of protoporphrinogen oxidase can be found (organized by mode of action) at https: / / www.weedscience.org / summary / MOA.aspx. Preferred PPO-resistant weeds are those selected from the group including Acalypha spp., Amaranthus spp., Ambrosia spp., Avena spp., Conyza spp., Descurainia spp., Eleusine spp., Euphorbia spp., Lolium spp., Poa spp., and Senecio spp.

[0050] Examples of weeds resistant to inhibition of protoporphyrinogen oxidase include, but are not limited to, Acalypha australis (Asian Capellleaf), Amaranthus hybridus (syn: quitensis) (Smooth Pigweed), Amaranthus palmeri (Palmer Amaranth), Amaranthus retroflexus (Redroot Pigweed), Amaranthus tuberculatus (Amaranthus rudis) (Tall / Common Waterhemp), Ambrosia artemisiifolia (Common Ragweed), Avena fatua (Wild Oat), Conyza sumatrensis (Sumatran Fleabane), Descurainia sophia (Flixweed), Eleusine indica (Goosegrass), Euphorbia heterophylla (Wild Poinsettia), Lolium rigidum (Rigid Ryegrass), Poa annua (Arabidopsis), and Senecio vernalis (Eastern Groundsel).

[0051] Preferably, the weed is resistant to inhibition of protoporphyrinogen oxidase and is derived from the Amaranthus species. More preferably, the weed resistant to inhibition of protoporphyrinogen oxidase is Amaranthus palmeri and / or Amaranthus tuberculatus.

[0052] Amaranthus palmeri is a species of edible flowering plant in the genus Amaranth. It has several common names including Palmer amaranth, carelessweed, dioecious amaranth, Palmer's amaranth, and Palmer's pigweed. Control of Amaranthus palmeri has become increasingly difficult for farmers due to its ability to multiply traits and thus quickly develop resistance to herbicides. As a result, Amaranthus palmeri has been described as the "king of weeds" in Chemical & Engineering News (2019), see volume 97, issue 31.

[0053] Amaranthus tuberculatus or Amaranthus tamariscinus, commonly known as rough-fruited amaranth, rough-fruited waterhemp, tall waterhemp, common waterhemp, or redroot pigweed, is a species of flowering plant. It is a summer annual broadleaf plant with a germination period lasting several months. Tall waterhemp is reported as a weed in 40 of the 50 states of the United States as of 2007.

[0054] The resistance mechanism of PPO inhibitor-resistant weeds to be controlled in the present invention may be site-of-action resistance due to site-of-action mutation, or may be non-site-of-action resistance independent of site-of-action mutation. Examples of site mutations include Arg128Leu, Arg128Met, Arg128Gly, Arg128His, Arg128Ala, Arg128Cys, Arg128Glu, Arg128Ile, Arg128Lys, Arg128Asn, Arg128Gln, Arg128Ser, Arg128Thr, Arg128Val, Arg128Tyr, Gly210 deletion, Ala210 deletion, Gly210Thr, Ala210Thr, G211 deletion, Gly114Glu, Ser149Ile, and Gly399Ala in PPO (all amino acid numbers are standardized to the sequence of PPO2 from Amaranthus palmeri).

[0055] PPO1 and PPO2 exist in the PPO of weeds, and mutations may occur in either or both of PPO1 and PPO2. The present invention is suitable as a method for controlling PPO inhibitor-resistant weeds having a mutation in PPO2.

[0056] For example, the Arg128Met mutation means that there is a mutation in the 128th amino acid. Examples of PPO inhibitor resistant weeds are as follows: Amaranthus palmeri is known to have the Arg128Met mutation in PPO2 (Pest Management Science 73, 1559-1563). Amaranthus palmeri is known to have the Arg128Gly mutation in PPO2 (Pest Management Science 73, 1559-1563). Waterhemp is known to have the Arg128Gly mutation in PPO2 (Pest Management Science, doi:10.1002 / ps.5445). Waterhemp with the Arg128Ile mutation in PPO2 and waterhemp with the Arg128Lys mutation in PPO2 are known (Pest Management Science, doi:10.1002 / ps.5445). Solanaceae with a mutation in PPO2 equivalent to Arg128His (Solanaceae with an Arg132His mutation in PPO2) are known (WSSA annual meeting, 2018). Palmer's Amaranthus palmeri with a Gly399Ala mutation in PPO2 is known (Frontiers in Plant Science 10, Article 568). Goosegrass with a mutation in PPO1 equivalent to Ala210Thr (goosegrass with an Ala212Thr mutation in PPO1) is known (WSSA annual meeting, 2019).

[0057] Also known are the double mutants K127N and 1130V (sometimes called the Lys127Asn, lle130Val double mutation) found in water chestnut (Amaranthus tuberculatus), and the A212T mutation (sometimes called the Ala212Thr mutation) found only in goosegrass (Eleusine indica) to date.

[0058] Thus, preferably, PPO-resistant weeds are weeds containing the AG210, R98L, R128G, R128M, G339A, K127N-I130V, A212T, Arg128His, Arg128Ile or Arg128Lys mutation in the Protox enzyme that confers resistance to PPO inhibitors.

[0059] The present invention effectively controls PPO inhibitor-resistant weeds having these point mutations, but is not limited thereto.

[0060] Populations of Amaranthus palmeri and Amaranthus tuberculatus have evolved as PPO-resistant weeds in many parts of the world. There are three documented mutations in the PPO enzyme that have been identified in Amaranthus species that confer resistance to PPO-inhibiting herbicides. First, a mutation at R128, most commonly to glycine or methionine, has been documented in both A. palmeri and A. tuberculatus. Second, a deletion of the amino acid G210 has been found in both important Amaranthus species. Third, a mutation at amino acid G399 associated with a change to alanine has been documented in A. palmeri.

[0061] The numbering of Amaranthus sequences (e.g., 98, 210, and 399) is based on NCBI reference DQ386114. Because PPO genes are variable in length not only depending on the weed species but also between individual plants from the same species, references in this application to amino acids 98, 210, and 399 include any equivalent amino acids when a different reference system is used.

[0062] Furthermore, R128 is sometimes referred to as R98 because the mutation was first found in Ambrosia and the same gene in that species (Ambrosia) lacks a 30 amino acid sequence at the beginning of the gene. That is, the locus of R128 is the same as R98, and the change in numbering is due to the presence of a 30 amino acid signal peptide in A. palmeri. Those skilled in the art will recognize this and know how to align various PPO sequences to determine the mutation location.

[0063] In one embodiment, the PPO-resistant weeds to be controlled are Acalypha australis (Asian Capellleaf), Amaranthus hybridus (syn:quitensis) (Smooth Pigweed), Amaranthus palmeri (Palmer Amaranth), Amaranthus retroflexus (Redroot Pigweed), Amaranthus tuberculatus (Amaranthus rudis) (Tall / Common Waterhemp), Ambrosia artemisiifolia (Common Ragweed), Avena fatua (Wild Oat), Conyza sumatrensis (Sumatran In accordance with the present invention, the plant is selected from the group consisting of: Eleusine indica (Goosegrass), Descurainia sophia (Flixweed), Eleusine indica (Goosegrass), Euphorbia heterophylla (Wild Poinsettia), Lolium rigidum (Rigid Ryegrass), Poa annua (Arabidopsis), and Senecio vernalis (Eastern Groundsel).

[0064] The PPO-resistant weeds to be controlled are preferably selected from Amaranthus hybridus (syn: quitensis) (Smooth Pigweed), Amaranthus palmeri (Palmer Amaranth), Amaranthus retroflexus (Redroot Pigweed), and Amaranthus tuberculatus (Amaranthus rudis) (Tall / Common Waterhemp).

[0065] More preferably, the PPO-resistant weeds to be controlled are Amaranthus palmeri (Palmer Amaranth) or Amaranthus tuberculatus (Amaranthus rudis) (Tall / Common Waterhemp).

[0066] In one embodiment, the PPO-resistant weed has a ΔG210, G399A, or R128 mutation in the protox enzyme that confers resistance to a PPO-inhibiting herbicide.

[0067] In one embodiment, the PPO-resistant weeds have a glycine amino acid at codon 128 of PPX2L instead of an arginine amino acid, i.e., the PPO-resistant weeds have an R128G mutation in the protox enzyme that confers resistance to PPO-inhibiting herbicides.

[0068] In one embodiment, the PPO-resistant weeds have a methionine amino acid at codon 128 of PPX2L instead of an arginine amino acid, i.e., the PPO-resistant weeds have an R128M mutation in the protox enzyme that confers resistance to PPO-inhibiting herbicides.

[0069] In one embodiment, the PPO-resistant weeds have a leucine amino acid at codon 128 of PPX2L instead of an arginine amino acid, i.e., the PPO-resistant weeds have an R128L mutation in the protox enzyme that confers resistance to PPO-inhibiting herbicides.

[0070] In one embodiment, the PPO-resistant weed has a codon deletion at position 210 of PPX2L. Preferably, the deleted codon is for a glycine amino acid.

[0071] In another embodiment, Amaranthus palmeri and / or Amaranthus tuberculatus have a glycine amino acid at codon 128 of the gene encoding the porphyrinogen oxidase enzyme. Preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have a glycine amino acid at codon 128 of PPX2L. More preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have a glycine amino acid instead of an arginine amino acid at codon 128 of PPX2L.

[0072] In another embodiment, Amaranthus palmeri and / or Amaranthus tuberculatus have a methionine amino acid at codon 128 of the gene encoding the porphyrinogen oxidase enzyme. Preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have a methionine amino acid at codon 128 of PPX2L. More preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have a methionine amino acid instead of an arginine amino acid at codon 128 of PPX2L.

[0073] In another embodiment, the weed has a codon deletion at position 210 in the gene encoding the porphyrinogen oxidase enzyme. Preferably, the weed has a codon deletion at position 210 in PPX2L. More preferably, the deleted codon is for the glycine amino acid.

[0074] In another embodiment, Amaranthus palmeri and / or Amaranthus tuberculatus have a codon deletion at position 210 in the gene encoding the porphyrinogen oxidase enzyme. Preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have a codon deletion at position 210 in PPX2L. More preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have a glycine amino acid deletion.

[0075] In another embodiment, the weed has an alanine amino acid at codon 399 of the gene encoding the porphyrinogen oxidase enzyme. Preferably, the weed has an alanine amino acid at codon 399 of PPO2. More preferably, the weed has an alanine amino acid at codon 399 of PPO2 instead of a glycine amino acid.

[0076] In another embodiment, Amaranthus palmeri and / or Amaranthus tuberculatus have an alanine amino acid at codon 399 of the gene encoding the porphyrinogen oxidase enzyme. Preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have an alanine amino acid at codon 399 of PPO2. More preferably, Amaranthus palmeri and / or Amaranthus tuberculatus have an alanine amino acid instead of a glycine amino acid at codon 399 of PPO2.

[0077] The weeds may be selected from the group consisting of Acalypha spp., Amaranthus spp., Ambrosia spp., Avena spp., Conyza spp., Descurainia spp., Euphorbia spp. and Senecio spp. Preferably, the weeds are Amaranthus spp. More preferably, the weeds are Amaranthus palmeri and / or Amaranthus tuberculatus.

[0078] The weeds of the present application should also be understood to include weeds that have been made tolerant to herbicides or classes of herbicides (e.g., ALS inhibitors, GS inhibitors, EPSPS inhibitors, PPO inhibitors, ACCase inhibitors, and HPPD inhibitors) by evolution, traditional breeding methods, or genetic engineering. Examples include Amaranthus palmeri, which has evolved resistance to glyphosate and / or acetolactate synthase (ALS)-inhibiting herbicides.

[0079] The present invention further provides a method for selectively controlling weeds in a locus containing useful (crop) plants and weeds, the method comprising applying to the locus a weed-controlling amount of a compound of formula (I) according to the present invention. By "control" is meant killing, reducing or retarding growth, or preventing or reducing germination. It is noted that the compounds of formula (I) show much improved selectivity compared to known structurally similar compounds. By "locus" is meant the area in which the plants are growing or will grow. Application can be applied to the locus before and / or after emergence of the crop plants. Some crop plants can be inherently resistant to the herbicidal effect of the compounds of formula (I).Within the scope of the present invention, the target crops and / or useful plants to be protected are typically berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fibre plants, such as cotton, flax, hemp, jute and sisal; agricultural crops, such as sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; and arable plants, such as bermuda grass, strawberry bush, bentgrass, centipede grass, fescue, ryegrass, lawn grass and wild grass. herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, squash, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as vines, for example grapes. Preferred crop plants include corn, cereals, soybeans, specialty crops, oil palm and cotton. Specialty crops include fruits and vegetables, tree nuts, dried fruits, and horticultural and nursery crops, including floriculture.

[0080] The application rate of the compound of formula I can vary within a wide range and can depend on the nature of the soil, the application method (pre-emergence or post-emergence; seed dressing; application to seed furrow; no tillage, etc.), the crop plant, the weeds to be controlled, the prevailing climatic conditions, as well as the application method, application time and other factors governed by the target crop. The compound of formula I according to the invention is generally applied at a rate of 10 g / ha to 1000 g / ha, in particular 25 g / ha to 500 g / ha, more particularly 50 g / ha to 250 g / ha, and even more particularly 50 g / ha to 200 g / ha. In a particularly preferred embodiment, the compound of formula (I) according to the invention is generally applied at a rate of 100 g / ha to 200 g / ha.

[0081] Application is generally by spraying the composition, typically over a wide area with a tractor-mounted sprayer, although other methods such as dusting (for dusts), drip or drench can also be used.

[0082] The term "useful plants" should also be understood to include useful plants in which resistance to herbicides such as bromoxynil or to a class of herbicides, such as 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, 5-enol-pyroyl-shikimate-3-phosphate-synthase (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen-oxidase (PPO) inhibitors, has been imparted by conventional breeding or genetic engineering methods. An example of a crop in which resistance to imidazolinones, such as imazamox, has been imparted by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered resistant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0083] The term "useful plants" should also be understood to include useful plants that have been transformed using recombinant DNA techniques with the ability to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly those from the genus Bacillus.

[0084] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Rootworm® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing CryIA(b) and CryIIIB(b1) toxins); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait), and Protecta®.

[0085] The compound of formula (I) can be used in unmodified form or preferably with adjuvants that are conventionally used in the formulation field to provide herbicidal compositions.Thus, the present invention further provides a herbicidal composition comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an adjuvant.Agriculturally acceptable carriers are, for example, carriers suitable for agricultural use.Agricultural carriers are well known in the art.

[0086] For this purpose, the compounds of formula (I) can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, direct-sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials. The application method, such as spraying, misting, dusting, scattering, coating, or pouring, as well as the type of composition, is selected according to the intended purpose and the current situation. The composition may also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, as well as fertilizers, sources of trace elements, or other compounds for obtaining special effects.

[0087] Suitable carriers and adjuvants, for example for use in agriculture, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0088] Suspension concentrates are aqueous formulations in which fine solid particles of the active compound are suspended. Such formulations contain anti-settling and dispersing agents and may further contain wetting agents to enhance activity, as well as anti-foaming agents and crystal growth inhibitors. In use, these concentrates are diluted in water and usually applied by spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0089] Wettable powders are in the form of fine particles that disperse easily in water or other liquid carriers. These particles contain the active ingredient held in a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica and other easily wet organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersing agents or emulsifying agents.

[0090] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist solely of the active compound and a liquid or solid emulsifier, or may contain a liquid carrier such as xylene, high boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and usually applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0091] Granular formulations include both extrudates and relatively coarse particles, and are usually applied undiluted to the area where treatment is required. Typical carriers for granular formulations include sand, Fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, ground corn cobs, ground peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations usually contain 5% to 25% active ingredient, which may include surfactants such as high-boiling aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or spreading agents such as dextrin, glue or synthetic resins.

[0092] Dusts are free-flowing admixtures of the active ingredient and finely divided solids such as talc, clays, powders and other organic and inorganic solids which act as dispersants and carriers.

[0093] Microcapsules are typically droplets or granules of active ingredient enclosed in an inert porous shell that allows the encapsulated material to be released into the environment at a controlled rate. The encapsulated droplets are typically 1-50 microns in diameter. The encapsulated liquid typically constitutes 50-95% of the capsule's weight and may contain a solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granule and retains the active species in liquid form within the pores of the granule. The granules are typically in the range of 1 millimeter to 1 centimeter in diameter, preferably 1-2 millimeters. Granules are formed by extrusion, agglomeration or prilling, or are natural. Examples of such materials are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xandates.

[0094] Other useful formulations for agricultural chemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes and other organic solvents in which complete dissolution at the desired concentration is achieved. Pressurized sprayers may also be used in which the active ingredient is dispersed in finely divided form as the low boiling dispersant solvent carrier evaporates.

[0095] Suitable agricultural adjuvants and carriers useful in formulating the compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0096] Liquid carriers that may be utilized include, for example, water, toluene, xylene, petroleum naphtha oil, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, kutadeca Examples of suitable solvents include ethyl acetate, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. For dilution of concentrates, water is the typical carrier of choice.

[0097] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut hulls, and lignin.

[0098] A wide range of surfactants may be advantageously utilized in both the liquid and solid compositions, particularly those designed to be diluted with a carrier prior to application. These surfactants, when used, typically comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be utilized as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylaryl sulfonate salts, such as calcium dodecylbenzene sulfonate; nonylphenol-C; 18 Alkylphenol-alkylene oxide adducts such as ethoxylates; Tridecyl alcohol-C 16 These include alcohol-alkylene oxide adducts such as ethoxylates; soaps such as sodium stearate; alkyl naphthalene sulfonates such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinates such as sodium di(2 ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryl trimethyl ammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphate esters.

[0099] Other adjuvants commonly utilized in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray size regulators, pigments, antioxidants, foaming agents, defoamers, light blocking agents, compatibilizers, antifoaming agents, sequestering agents, neutralizing and buffering agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, trace elements, emollients, lubricants and adhesives.

[0100] The compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to the crop area or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these preparations, if desired with further carriers, surfactants or application-promoting adjuvants customarily used in the field of formulations. Furthermore, the herbicidal compounds of the present invention can also be used in mixtures with one or more further herbicides and / or plant growth regulators. EXAMPLES

[0101] The following examples serve to illustrate the invention.

[0102] Formulation examples

[0103] [Table 2]

[0104] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to obtain wettable powders which can be diluted with water to obtain a suspension of the desired concentration.

[0105] [Table 3]

[0106] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0107] emulsifiable concentrate Active ingredient [compound of formula (I)] 10% Octylphenol polyethylene glycol ether 3% (Ethylene oxide 4-5 mol) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (ethylene oxide 35 mol) 4% Cyclohexanone 30% Xylene Mixture 50%

[0108] Emulsions of any required dilution which can be used for plant protection can be obtained from this concentrate by dilution with water.

[0109] [Table 4]

[0110] Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used in dry dressings for seeds.

[0111] Extruder Granules Active ingredient [compound of formula (I)] 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0112] The active ingredient is mixed and ground with the adjuvants, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0113] Coated Granules Active ingredient [compound of formula (I)] 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0114] The finely ground active ingredient is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol, thus obtaining non-dusty coated granules.

[0115] Suspension concentrate Active ingredient [compound of formula (I)] 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (ethylene oxide 15 mol) 6% Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0116] The finely ground active ingredient is mixed homogeneously with the auxiliaries to obtain a suspension concentrate, which can be diluted with water to obtain any desired concentration, and can be used to treat and protect living plants and plant propagation material from microbial infestation by spraying, pouring or immersion.

[0117] Flowable concentrate for seed treatment Active ingredient [compound of formula (I)] 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol with 10-20 moles EO 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0118] The finely ground active ingredient is mixed homogeneously with the auxiliaries to obtain a suspension concentrate, which can be diluted with water to obtain any desired concentration, and can be used to treat and protect living plants and plant propagation material from microbial infestation by spraying, pouring or immersion.

[0119] Slow-release capsule suspension 28 parts of the combined compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenylisocyanate mixture (8:1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer, and 51.6 parts of water until the desired particle size is achieved. To the emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete.

[0120] The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The medium capsule size is 8-15 microns.

[0121] The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for the purpose.

[0122] Biological Examples Example 1: Control of plants carrying a mutation at codon 128 with postemergence applied PPO herbicides To determine the effect of mutations at codon 128 of PPX2L from wild-type arginine to glycine or methionine, the commercial standard PPO inhibitor fomesafen and compound 8 of the present application were applied to three Amaranthus palmeri populations.

[0123] Three A. palmeri populations were used: a known PPO inhibitor sensitive population ("sensitive"), a population in which individuals are known to be homozygous for glycine at codon 128 of the protoporphyrinogen oxidase gene PPX2L ("128G"), and a population in which individuals are known to be homozygous for methionine at codon 128 of the protoporphyrinogen oxidase gene PPX2L ("128M").

[0124] Seeds were sown in seed trays containing Ericaceae compost and covered with vermiculite. Plants approximately 1 inch tall were transplanted, one per pot, into 3 inch diameter pots containing Ericaceae compost. Pots were watered and maintained in the greenhouse at 180 μmol m -2 s -1 The plants were given a 16H photoperiod, 24°C day and 18°C ​​night temperatures, and 65% relative humidity to a height of 3 inches, at which point the herbicides were applied to 14 individual plants per rate of each biotype at the application rates specified in Table 1 below.

[0125] All treatments were applied as dilutions in reverse osmosis water at 0.5% by volume with the commercial adjuvant Adigor®. Prior to dilution with water, compound 8 was first dissolved to a 5% solution in a solvent mixture containing 11.12% Emulsogen EL360, 44.44% Dowanol DPM, and 44.44% N-methylpyrrolidone. Herbicide applications consisted of herbicide treatments at 200 L / ha. -1 The application was performed with a track sprayer having a flat fan nozzle applied at a rate of 1000 ml.

[0126] After treatment, plants were watered and maintained in a greenhouse at 180 μmol m -2 s -1 and a 16H photoperiod of 24° C. day and 18° C. night temperatures and 65% relative humidity until 14 days after application, at which point the plants were rated on the basis of "dead or alive." Plants still alive at this point were classified as surviving the herbicide application, and the average results of this rating are shown in Table 1.

[0127] [Table 5]

[0128] conclusion Compound 8 showed similar ability to fomesafen in controlling "susceptible" populations, with both herbicides achieving 8 g ai / ha. -1 However, surprisingly, compound 8 achieved complete control of this population (i.e., no surviving plants) at a rate of 16 g ai / ha.-1 showed the ability to achieve complete control of both 128G and 128M at rates of 128 g ai / ha, whereas fomesafen was able to achieve complete control at rates of 128 g ai / ha. -1 It can only achieve complete control with 128M at a rate of 128g ai / ha. -1 However, only 5 / 14 of the "128G" individuals were able to be killed.

[0129] Example 2: Control of plants carrying a mutation at codon 210 with postemergence applied PPO herbicides The commercial standard PPO inhibitor fomesafen and compound 8 of the present application were applied to a PPO inhibitor herbicide resistant Amaranthus tuberculatus population. In particular, each individual plant of the A. tuberculatus population was known to be homozygous for a deletion of a glycine residue at codon 210 of the protoporphyrinogen oxidase gene PPX2L.

[0130] Seeds were sown in seed trays containing Ericaceae compost and covered with vermiculite. Plants approximately 1 inch tall were transplanted, one per pot, into 3 inch diameter pots containing Ericaceae compost. Pots were watered and maintained in the greenhouse at 180 μmol m -2 s -1 The plants were given a 16H photoperiod of 24°C day and 18°C ​​night temperatures and 65% relative humidity to a height of 3 inches, at which point the herbicides were applied to 16 individual plants per rate at the rates specified in Table 2 below.

[0131] All treatments were applied as dilutions in reverse osmosis water at 1% by volume with the commercial adjuvant Agridex®. Prior to dilution with water, compound 8 was first dissolved to a 5% solution in a solvent mixture containing 11.12% Emulsogen EL 360, 44.44% Dowanol DPM, and 44.44% N-methylpyrrolidone. Herbicide applications consisted of herbicide treatments at 200 L / ha. -1 The application was performed with a track sprayer having a flat fan nozzle applied at a rate of 1000 ml.

[0132] After treatment, plants were watered and maintained in a greenhouse at 180 μmol m -2 s -1 and a 16H photoperiod of 24° C. day and 18° C. night temperatures and 65% relative humidity until 14 days after application, at which point the plants were rated on the basis of "dead or alive." Plants still alive at this point were classified as surviving the herbicide application, and the average results of this rating are shown in Table 2.

[0133] [Table 6]

[0134] conclusion Surprisingly, compound 8 showed superior control of PPO inhibitor herbicide-resistant Amaranthus tuberculatus with a mutation at codon 210 compared to fomesafen, especially at application rates of at least 8 to 105 g / ha. -1 No plants survived at these applications of compound 8. This was at 210 g ai / ha. -1 This is in comparison to fomesafen, where no plants survived after these applications.

[0135] Example 3: Control of plants with a mutation at codon 210 by PPO herbicides in field trials Field trials were conducted in plots in Illinois USA where A. tuberculatus is inhabited, approximately 60-70% of which contain the ΔG210 mutation.

[0136] The study was laid out as a randomized complete block design with two replications per treatment. Plot size per replication was 10 m. 2Compound 8 and commercial standard PPO herbicides (saflufenacil, fomesafen, glyphosate, glufosinate, thiafenacil) were applied to A. tuberculatus plants approximately 4 inches tall using a water volume of 300 l / ha. The efficacy of the tested compounds was visually assessed 14 days after application and expressed as % weed control, with a range of ratings, 100% being complete control and 0% representing weed populations / growth similar to those observed in untreated checks. Only species present at sufficient density and consistency for a reliable assessment were evaluated. Results are shown in Table 3.

[0137] [Table 7]

[0138] conclusion Example 3 demonstrates that compound 8 provides excellent weed control of PPO inhibitor herbicide resistant A. tuberculatus at all test rates between 50 and 200 g AI / ha. Efficacy is particularly strong (>90%) at application rates between 100 and 200 g AI / ha. Surprisingly, compound 8 is clearly superior to all standard commercial products, including saflufenacil, fomesafen, glyphosate, glufosinate, and thiafenacil, at all test rates between 50 and 200 g AI / ha.

Claims

1. 1. A method for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds, comprising administering to the weeds, parts of the weeds, weed propagation material, or the locus of the weeds an effective amount of a compound represented by formula (I): 【Chemistry 1】 (In the formula, Each R 1 and R 2 is selected from the group consisting of hydrogen and halogen; R 3 is hydrogen, C 1 ~C 4 Alkyl, CO 2 R 5 and C.H. 2 OR 6 is selected from the group consisting of R 4 is hydrogen and C 1 ~C 4 is selected from the group consisting of alkyl, R 5 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Alkenyl, C 3 ~C 6 Alkynyl, C 1 ~C 4 Alkoxy C 1 ~C 4 Alkyl, C 1-4 Alkyl carbonyl C 1-4 Alkyl and Heterocyclyl C 1 ~C 3 is selected from the group consisting of alkyl, R 6 is C 1 ~C 2 Alkylsulfonyl, C 1 ~C 4 Alkylcarbonyl and C 3 ~C 4 cycloalkylcarbonyl; R 7 is hydrogen, C 1 ~C 4 Alkyl and C 1 ~C 4 haloalkyl; R 8 is hydrogen, amino, C 1 ~C 6 Alkyl, C 3 ~C 6 Alkenyl and C 3 ~C 6 alkynyl) applying a compound of The PPO-resistant weeds are weeds that are resistant to at least one PPO-inhibiting herbicide, except for the compound of formula (I); method.

2. 2. The method of claim 1, wherein the PPO-resistant weed has a mutation at amino acid 128 and / or amino acid 210 of the gene encoding the protoporphyrinogen oxidase enzyme.

3. 3. The method of claim 1 or 2, wherein the PPO-resistant weed has a glycine amino acid at codon 128 of the gene encoding the protoporphyrinogen oxidase enzyme.

4. 3. The method of claim 1 or 2, wherein the PPO-resistant weed has a methionine amino acid at codon 128 of the gene encoding the protoporphyrinogen oxidase enzyme.

5. 3. The method of claim 1 or 2, wherein the PPO-resistant weed has a codon deletion at position 210 of the gene encoding the protoporphyrinogen oxidase enzyme.

6. The method of claim 5, wherein the deleted codon is for a glycine amino acid.

7. 7. The method of any one of claims 1 to 6, wherein the PPO-resistant weeds are selected from the group consisting of Acalypha spp., Amaranthus spp., Ambrosia spp., Avena spp., Conyza spp., Descurainia spp., Euphorbia spp., and Senecio spp.

8. The method of any one of claims 1 to 6, wherein the PPO-resistant weeds are Amaranthus species.

9. 7. The method of any one of claims 1 to 6, wherein the PPO-resistant weeds are selected from the group consisting of Amaranthus palmeri and Amaranthus tuberculatus.

10. The method according to any one of claims 1 to 9, wherein the compound of formula (I) is applied as part of an agrochemical composition comprising at least one further compound: a herbicide B.

11. 11. The method of claim 10, wherein the herbicide B is selected from the group consisting of S-metolachlor, glufosinate, L-glufosinate, glyphosate, mesotrione, bicyclopyrone and metribuzin.

12. A method according to any one of claims 1 to 11, wherein the compound of formula (I) is applied as part of an agrochemical composition further comprising an agrochemically acceptable diluent or carrier.

13. The method according to any one of claims 1 to 12, wherein the compound of formula (I) is applied in an amount of from 50 g / ha to 200 g / ha.

14. 2. Use of the compounds of formula (I) as defined in claim 1 for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide resistant weeds.

15. 15. The use according to claim 14, wherein the protoporphyrinogen IX oxidase (PPO) inhibitor herbicide resistant weeds have a mutation at amino acid 128 and / or amino acid 210 of the gene encoding the protoporphyrinogen oxidase enzyme.

16. Use of a composition according to any one of claims 10 to 12 for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide resistant weeds.

17. 17. The use according to claim 16, wherein the protoporphyrinogen IX oxidase (PPO) inhibitor herbicide resistant weeds have a mutation at amino acid 128 and / or amino acid 210 of the gene encoding the protoporphyrinogen oxidase enzyme.

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