Method for controlling weeds

Abstract

The present invention relates to a method for controlling the growth of a weed of an antigenic porphyrinogen IX oxidase (PPO) inhibitor herbicide, comprising applying to the weed, a portion of the weed, weed propagation material, or a locus of the weed an effective amount of a compound of formula (I) wherein the substituents are as defined in claim 1, and wherein the PPO resistant weeds are weeds that are resistant to at least one PPO inhibiting herbicide other than the compound of formula (I). # imgabs0 #

Description

[0001] The present invention relates to a method for controlling the growth of weeds that are resistant to porphyrinogen IX oxidase (PPO) inhibitor herbicides, the method comprising applying to the weeds, a part of the weeds, the weed propagation material, or the locus of the weeds an effective amount of a compound of formula (I), and wherein the PPO-resistant weeds are weeds that are resistant to at least one PPO-inhibiting herbicide other than the compound of formula (I).

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

[0003] Herbicide resistance has been known since the 1950s. Herbicide-resistant weeds, for example those resistant to PPO inhibitor herbicides (e.g., Acalypha spp., Amaranthus spp., Ambrosia spp., Avena spp., Conyza spp., Descurainia spp., Euphorbia spp., and Senecio spp.) present serious problems for efficient weed control, as such resistant weeds are becoming more widespread and, where resistant weeds are present, applications of the affected herbicides are far less effective than would normally be expected. In particular, weeds resistant to PPO inhibitor herbicides, like Amaranthus palmeri and Amaranthus tuberculatus, are a big problem for farmers in many parts of the world. In addition, the proportion of herbicide-resistant individuals increases over time due to selection pressure under repeated application of a herbicide mode of action (MOA) group.

[0004] The main mechanism of action of PPO inhibitor herbicides is to inhibit protoporphyrinogen oxidase (PPO), which is an enzyme that oxidizes protoporphyrinogen IX (PPGIX) in chloroplast cells to produce protoporphyrin IX (PPIX). PPIX is important because it is a precursor molecule for both chlorophyll (required for photosynthesis) and heme (required for the electron transport chain). However, PPO enzyme inhibitors are not just to prevent the production of chlorophyll and heme. PPO inhibition by PPO inhibitors has caused the accumulation of protoporphyrinogen IX, which infiltrates into the cytosol. The presence of protoporphyrinogen IX in the cytosol (acting as a photosensitizer) causes the formation of reactive oxygen species, which attack and destroy lipid membranes, causing cell death.

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

[0006] In crop protection, it is desirable to increase the specificity and reliability of action of active compounds, and in particular it is desirable for crop protection products to be tolerated by useful plants while being effective for controlling harmful weeds.

[0007] Therefore, there is a need for novel methods for effectively controlling herbicide-resistant weeds, in particular weeds resistant to PPO inhibitor herbicides, which methods are at the same time tolerated by useful plants and crops in the same field.

[0008] Surprisingly it has been found that compounds of formula (I) provide highly 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 weeds that are resistant to porphyrinogen IX oxidase (PPO) inhibitor herbicides, the method comprising applying to the weeds, a part of the weeds, the weed propagation material, or the locus of the weeds an effective amount of a compound having formula (I)

[0010]

[0011] in

[0012] R 1 and R 2 each selected from the group consisting of: hydrogen and halogen;

[0013] R 3 Selected from the group consisting of: hydrogen, C 1 -C 4 Alkyl, CO 2 R 5 and CH 2OR 6 ;

[0014] R 4 Selected from the group consisting of: hydrogen and C 1 -C 4 alkyl;

[0015] R 5 Selected from the group consisting of: 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 Alkylcarbonyl C 1-4 Alkyl and heterocyclic C 1 -C 3 alkyl;

[0016] R 6 Selected from the group consisting of: C 1 -C 2 Alkylsulfonyl, C 1 -C 4 Alkylcarbonyl and C 3 -C 4 Cycloalkylcarbonyl;

[0017] R 7 Selected from the group consisting of: hydrogen, C 1 -C 4 Alkyl and C 1 -C 4 Haloalkyl;

[0018] R 8 Selected from the group consisting of: hydrogen, amino, C 1 -C 6 Alkyl, C 3 -C 6 Alkenyl and C 3 -C 6 alkynyl; and

[0019] Wherein the weeds resistant to PPO are weeds resistant to at least one PPO inhibiting herbicide other than the compound of formula (I). According to a second aspect of the present invention, a kind of agrochemical composition is provided, the agrochemical composition comprises 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, fluazifop-dopamine or metribuzin.

[0020] According to a third aspect of the present invention, there is provided a method for controlling or preventing the undesirable plant growth of weeds having a mutation at amino acid 128, amino acid 210, or amino acid 399 in a gene encoding a protoporphyrinogen oxidase enzyme, wherein a herbicidally effective amount of a compound of formula (I) or a composition comprising the compound as an active ingredient is applied to weeds, a part of weeds, weed propagation material or a site of weeds. Preferably, there is provided a method for controlling or preventing the undesirable plant growth of weeds having a mutation at amino acid 128 and / or amino acid 210 in a gene encoding a protoporphyrinogen oxidase enzyme, wherein a herbicidally effective amount of a compound of formula (I) or a composition comprising the compound as an active ingredient is applied to weeds, a part of weeds, weed propagation material or a site of weeds.

[0021] 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 weeds that are antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides. In particular, there is provided the use of a compound of formula (I) for controlling the growth of weeds that are antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides, wherein the weeds of these antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides have mutations at amino acid 128, amino acid 210, and / or amino acid 399 in a gene encoding a protoporphyrinogen oxidase enzyme. Preferably, there is provided the use of a compound of formula (I) for controlling the growth of weeds that are antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides, wherein the weeds of these antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides have mutations at amino acid 128 and / or amino acid 210 in a gene encoding a protoporphyrinogen oxidase enzyme.

[0022] According to a fifth aspect of the present invention, there is provided an agrochemical composition comprising a compound of formula (I) for controlling the growth of weeds that are antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides. In particular, there is provided a composition comprising a compound of formula (I) for controlling the growth of weeds that are antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides, wherein the weeds of these antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides have mutations at amino acid 128, amino acid 210, and / or amino acid 399 in a gene encoding a protoporphyrinogen oxidase enzyme. Preferably, there is provided a composition comprising a compound of formula (I) for controlling the growth of weeds that are antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides, wherein the weeds of these antigenic to porphyrinogen IX oxidase (PPO) inhibitor herbicides have mutations at amino acid 128 and / or amino acid 210 in a gene encoding a protoporphyrinogen oxidase enzyme.

[0023] The presence of one or more possible asymmetric carbon atoms in a compound with formula (I) means that the compound can exist in the form of chiral isomers, i.e., enantiomers or diastereomers. As a result of restricted rotation around a single bond, atropisomers may also exist. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof of compounds with formula (I). Similarly, formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) (when present). The present invention includes all possible tautomeric forms of compounds with formula (I). Similarly, in the presence of disubstituted olefins, these can exist in E or Z form or as a mixture of the two in any ratio. The present invention includes all these possible isomeric forms and mixtures thereof of compounds with formula (I).

[0024] The compound of formula (I) will generally be provided in the form of an agronomically acceptable salt, zwitterion or an agronomically acceptable zwitterionic salt. The present invention encompasses all such agronomically acceptable salts, zwitterions and mixtures thereof in all ratios.

[0025] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo).

[0026] As used herein, amino means -NH 2 Group.

[0027] As used herein, the term “C 1- C 6"Alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and attached to the remainder of the molecule by a single bond. 1- C 4 "Alkyl" should be interpreted accordingly. 1- C 6 Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and isomers thereof, such as isopropyl, isobutyl, sec-butyl, tert-butyl or isopentyl.

[0028] As used herein, the term “C 2- C 6 "Alkenyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing at least one double bond which may be of (E) or (Z) configuration, having from two to six carbon atoms, attached to the remainder of the molecule by a single bond. 3- C 6 Alkenyl should be interpreted accordingly. 2- C 6 Examples of alkenyl groups include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.

[0029] As used herein, the term “C 2- C 6 "Alkynyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and attached to the remainder of the molecule by a single bond. 3- C 6 "Alkynyl" should be interpreted accordingly. 2- C 6 Examples of alkynyl groups include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

[0030] As used herein, the term “C 1- C 6 "Haloalkyl" refers to a C group as generally defined above which is substituted by one or more halogen atoms which may be the same or different. 1- C 6 Alkyl group. 1- C 4 Haloalkyl should be interpreted accordingly. 1- C 6 Examples of haloalkyl include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0031] As used herein, the term “C 1- C 4 Alkoxy C1- C 4 "Alkyl" refers to a group having the formula R b -OR a - a group, wherein R b is C as defined above 1- C 4 alkyl group, and R a is C as defined above 1-4 Alkylene group.

[0032] As used herein, the term “C 1- C 4 Alkylcarbonyl C 1- C 4 "Alkyl" refers to a group having the formula -R b C(O)R a A group in which R a is C as defined above 1- C 4 Alkyl, and R b is C as defined above 1-4 Alkylene group.

[0033] As used herein, the term "heterocyclyl" or "heterocyclic" refers to a stable 5- or 6-membered non-aromatic monocyclic group containing 1, 2, or 3 heteroatoms individually selected from nitrogen, oxygen, and sulfur. The heterocyclyl group may be bonded to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl groups include, but are not limited to, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolanyl, morpholinyl, oxazininyl, oxetanyl, or δ-lactamyl.

[0034] As used herein, the term "heterocyclyl C 1- C 2 "Alkyl" means a C 1- C 2 The alkylene group is attached to the heterocyclic ring of the rest of the molecule.

[0035] As used herein, the term “C 1-6 "Alkylsulfonyl" refers to a group having the formula -S(O) 2 R a A group in which R a is C as defined above 1-6 The term "C 1-2 "Alkylsulfonyl" should be interpreted accordingly.

[0036] As used herein, the term “C 1- C 4 "Alkylcarbonyl" refers to a group having the formula Ra C(O)-, where R a is C as defined above 1- C 4 Alkyl group.

[0037] As used herein, the term “C 3- C 8 "Cycloalkyl" refers to a stable monocyclic group which is saturated and contains 3 to 8 carbon atoms. 3- C 8 Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0038] As used herein, the term “C 3- C 8 "Cycloalkylcarbonyl" refers to a group having the formula R a C(O)-, where R a is C as defined above 3- C 8 Cycloalkyl group. 3- C 4 Cycloalkylcarbonyl should be interpreted accordingly.

[0039] As used herein, the terms "PPO inhibitor herbicide-resistant weeds," "PPO-inhibiting herbicide-resistant weeds," "PPO inhibitor-resistant weeds," "PPO-resistant weeds," "antigenic porphyrinogen IX oxidase inhibitor herbicide weeds," "antigenic porphyrinogen IX oxidase inhibiting herbicide weeds," "antigenic porphyrinogen oxidase inhibitor herbicide weeds," and "antigenic porphyrinogen oxidase inhibiting herbicide weeds" are synonymous and refer to plants that have inherited, developed or acquired the ability to, in response to treatment with appropriate or excessive rates of application of PPO-inhibiting herbicides:

[0040] (1) survive the treatment if the treatment is one that eradicates wild-type weeds; or

[0041] (2) Exhibit significant vegetative growth or vigorous growth after the treatment, if the treatment is one that inhibits the growth of wild-type weeds.

[0042] PPO-resistant weeds are weeds which cannot be controlled by application of known PPO inhibitor herbicides other than compounds of formula (I), whereas sensitive biotypes are controlled at those application rates.

[0043] Suitable agronomically acceptable salts of the present invention may have 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, phenethylbenzylamine, 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, heptadecanamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine , lysine, 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, stearamide, 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, tributylsulfoxide, triethylsulfonium, triethylsulfoxide, trimethylsulfonium, trimethylsulfoxide, tripropylsulfonium, and tripropylsulfoxide.

[0044] Suitable agronomically acceptable salts of the present invention may have 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, phenethylbenzylamine, 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, heptadecanamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine , lysine, 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, stearamide, 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, tributylsulfoxide, triethylsulfonium, triethylsulfoxide, trimethylsulfonium, trimethylsulfoxide, tripropylsulfonium, and tripropylsulfoxide.

[0045] The following list provides information on the substituents R of the compounds of formula (I) according to the present invention. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0046] 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 1Selected from the group consisting of: chlorine and fluorine.

[0047] R 2 is selected from the group consisting of hydrogen and halogen. 2 Selected from the group consisting of: chlorine and bromine.

[0048] R 3 Selected from the group consisting of: hydrogen, C 1 -C 4 Alkyl, CO 2 R 5 and CH 2 OR 6 Preferably, R 3 Selected from the group consisting of: CO 2 R 5 and CH 2 OR 6 More preferably, R 3 It is CO 2 R 5 .

[0049] R 4 Selected from the group consisting of: hydrogen and C 1 -C 4 More preferably, R 4 Selected from the group consisting of: hydrogen and C 1 -C 2 alkyl.

[0050] R 5 Selected from the group consisting of: 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 Alkylcarbonyl C 1- C 4 Alkyl and heterocyclic C 1 -C 3 Preferably, R 5 Selected from the group consisting of: H, CH 3 , C 2 H 5 , CH 3 CH 2 CH 2 , CH3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CH, (CH 3 ) 2 CHCH 2 , (CH 3 ) 3 C. CF 3 CH 2 , allyl, propargyl, CH 3 OCH 2 CH 2 , C 2 H 5 OCH 2 CH 2 , CH 3 CO 2 CH 2 CH 2 More preferably, R 5 Selected from the group consisting of: hydrogen and C 1 -C 4 alkyl.

[0051] R 6 Selected from the group consisting of: C 1 -C 2 Alkylsulfonyl, C 1 -C 4 Alkylcarbonyl and C 3 -C 4 Preferably, R 6 Selected from the group consisting of: C 1 -C 2 Alkylsulfonyl, C 1 -C 4 Alkylcarbonyl and cyclopropylcarbonyl.

[0052] R 7 Selected from the group consisting of: hydrogen, C 1 -C 4 Alkyl and C 1 -C 4 Preferably, R 7 Selected from the group consisting of: C 1 -C 4 More preferably, R 7 It is CF 3 .

[0053] R 8 Selected from the group consisting of: hydrogen, amino, C 1 -C6 Alkyl, C 3 -C 6 Alkenyl and C 3 -C 6 Preferably, R 8 It is C 1 -C 4 More preferably, R 8 Yes CH 3 .

[0054] A subgroup of preferred compounds are the following compounds, in which: R 1 is selected from the group consisting of: hydrogen, chlorine and fluorine; R 2 Selected from the group consisting of: chlorine and bromine; R 3 Selected from the group consisting of: CO 2 R 5 and CH 2 OR 6 ; R 4 Selected from the group consisting of: H, CH 3 and C 2 H 5 ; R 5 Selected from the group consisting of: H, CH 3 , C 2 H 5 , CH 3 CH 2 CH 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CH, (CH 3 ) 2 CHCH 2 , (CH 3 ) 3 C. CF 3 CH 2 , allyl, propargyl, CH 3 OCH 2 CH 2 , C 2 H 5 OCH 2 CH 2 , CH 3 CO 2 CH 2 CH 2 and tetrahydrofuranylmethyl; R 6 Selected from the group consisting of: C 1 -C 4 Alkylcarbonyl, cyclopropylcarbonyl and C1 -C 2 Alkylsulfonyl; R 7 It is CF 3 ; and R 8 Yes CH 3 .

[0055] A subgroup of more preferred compounds are the following compounds, in which: R 1 is selected from the group consisting of: hydrogen, chlorine and fluorine; R 2 Selected from the group consisting of: chlorine and bromine; R 3 It is CO 2 R 5 ; R 4 Selected from the group consisting of: H, CH 3 and C 2 H 5 ; R 5 Selected from the group consisting of: H, CH 3 , C 2 H 5 , CH 3 CH 2 CH 2 , CH 3 CH 2 CH 2 CH 2 , (CH 3 ) 2 CH, (CH 3 ) 2 CHCH 2 and (CH 3 ) 3 C; R 7 It is CF 3 ; and R 8 Yes CH 3 .

[0056] A subgroup of still more preferred compounds are the following compounds, in which: R 1 is selected from hydrogen, chlorine and fluorine; R 2 is selected from chlorine and bromine; R 3 It is CO 2 R 5 ; R 4 is methyl; R 7 is trifluoromethyl; and R 8 is methyl. Two particularly preferred compounds are those wherein R 1 is selected from chlorine and fluorine; R 2 is chlorine; R 3 It is CO 2 R 5 ; R 4 is methyl; R7 is trifluoromethyl; and R 8 It's methyl.

[0057] Most preferably, the compound of formula (I) is ethyl 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-carboxylate (also referred to herein as 'Compound 8').

[0058] Instance table

[0059] This table discloses specific compounds of formula (I) wherein R 7 is trifluoromethyl and R 8 It's methyl.

[0060]

[0061]

[0062] A list of weeds resistant to inhibition of protoporphyrinogen oxidase (organized by mode of action) can be found at https: / / www.weedscience.org / summary / MOA.aspx Preferred PPO-resistant weeds are those selected from the group consisting of Amaranthus spp., Amaranthus spp., Ambrosia spp., Avena spp., Ligusticum spp., Descurainia spp., Eleusine spp., Euphorbia spp., Lolium spp., Poa spp. and Senecio spp.

[0063] Examples of weeds resistant to protoporphyrinogen oxidase inhibition include, but are not limited to, Amaranthus tricolor (Asian Amaranthus tricolor), Amaranthus quinquefolius (Synonym: quitensis) (Smooth Pigweed), Palmer Amaranth, Amaranthus retroflexus (Redroot Pigweed), Amaranthus scabra (Western Amaranth) (Tall / Common Water Hemp), Ambrosia truncatula (Common Ragweed), Avena sativa (Wild Oats), Sumatran Fleabane, Flixweed, Goosegrass (Cricket Grass), Poinsettia leucophylla (Wild Poinsettia), Rigid Ryegrass, Poa annua (Annual Bluegrass), and Senecio vernalis (Eastern Groundsel).

[0064] Preferably, the weeds resistant to protoporphyrinogen oxidase inhibition are from the genus Amaranthus. More preferably, the weeds resistant to protoporphyrinogen oxidase inhibition are Palmer amaranth and / or Amaranthus sclerocarpa.

[0065] Palmer amaranth is an edible flowering plant species in the genus Amaranth. It has several common names, including Palmer amaranth, carelessweed, dioecious amaranth, Palmer's amaranth, and Palmer's pigweed. Palmer amaranth is becoming increasingly difficult for farmers to control because of its ability to proliferate and therefore quickly develop resistance to herbicides. As a result, Palmer amaranth was described as the "king of weeds" in Chemical & Engineering News in 2019 (see Vol. 97, No. 31).

[0066] Amaranthus tamariscinus (commonly known as roughfruit amaranth, rough-fruited water-hemp, tall water-hemp, common water-hemp) or redroot hogweed is a flowering plant species. It is an annual broadleaf weed that grows in the summer, with a sprouting period that lasts for several months. As of 2007, tall water-hemp is reported as a weed in 40 of the 50 states.

[0067] The resistance mechanism of the weeds resistant to PPO inhibitors to be controlled in the present invention may be due to site resistance caused by site mutation or non-site resistance unrelated to site mutation. The site mutations include Arg128Leu, Arg128Met, Arg128Gly, Arg128His, Arg128Ala, Arg128Cys, Arg128Glu, Arg128Ile, Arg128Lys, Arg128Asn, Arg128Gln, Arg128Ser, Arg128Thr, Arg128Val, Arg128Tyr, Gly210 deficiency, Ala210 deficiency, Gly210Thr, Ala210Thr, G211 deficiency, Gly114Glu, Ser149Ile and Gly399Ala of PPO (amino acid numbers are standardized in the PPO2 sequence of Amaranthus oleraceus).

[0068] Although PPO1 and PPO2 exist in the PPO of a weed, the mutation may be in PPO1 or PPO2, or both. The present invention is suitable as a method for controlling weeds having a mutation in PPO2 that is resistant to PPO inhibitors.

[0069] For example, an Arg128Met mutation means that there is a mutation in the 128th amino acid. The following are examples of weeds that are resistant to PPO inhibitors. Palmer amaranth with an Arg128Met mutation in PPO2 is known (Pest Management Science 73, 1559-1563). Palmer amaranth with an Arg128Gly mutation in PPO2 is known (Pest Management Science 73, 1559-1563). Water hemp with an Arg128Gly mutation in PPO2 is known (Pest Management Science, doi: 10.1002 / ps.5445). Water hemp with an Arg128Ile mutation in PPO2 and water hemp with an Arg128Lys mutation in PPO2 are known (Pest Management Science, doi: 10.1002 / ps.5445). Solanaceae with a mutation corresponding to Arg128His in PPO2 (Solanaceae with Arg132His mutation in PPO2) is known (WSSA Annual Meeting, 2018). Palmer amaranth with a Gly399Ala mutation in PPO2 is known (Frontiers in Plant Science 10, article 568). Glechoma longituba with a mutation corresponding to Ala210Thr in PPO1 (Glechoma longituba with Ala212Thr mutation in PPO1) is known (WSSA Annual Meeting, 2019).

[0070] The double mutants K127N, 1130V (sometimes also referred to as Lys127Asn, lle130Val double mutation) found in Amaranthus sclerocarpa and the A212T mutation (sometimes also referred to as Ala212Thr mutation) currently only found in Glechoma longituba are known.

[0071] Thus, preferably, PPO resistant weeds are weeds containing AG210, R98L, R128G, R128M, G339A, K127N-I130V, A212T, Arg128His, Arg128Ile or Arg128Lys mutations in the protoporphyrinogen oxidase enzyme conferring resistance to PPO inhibitors.

[0072] The present invention is effective in controlling, but not limited to, weeds resistant to PPO inhibitors having these point mutations.

[0073] Palmer amaranth and Amaranthus sclerosus populations have evolved to become PPO-resistant weeds in many areas of the world. There are three documented mutations in the PPO enzyme that have been identified as conferring resistance to PPO-inhibiting herbicides in Amaranthus species. First, a mutation at R128 (most commonly to glycine or methionine) has been documented in both Palmer amaranth and Amaranthus sclerosus. Second, a deletion of amino acid G210 has been found in both of these key Amaranthus species. Third, a mutation at amino acid G399 has been documented in Palmer amaranth that is associated with a change to alanine.

[0074] The numbering of the Amaranth sequences (e.g., 98, 210, and 399) is based on NCBI reference DQ 386114. Since PPO genes are variable in length not only according to the weed species, but also between individual plants from the same species, any reference to amino acids 98, 210, and 399 in this application includes any equivalent amino acid where a different reference system is used.

[0075] Additionally, R128 is sometimes referred to as R98 because the mutation was originally 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 R128 locus is identical to R98; the numbering change is due to the presence of a 30-amino acid signal peptide in Palmer amaranth. The skilled artisan is aware of this and knows how to align the various PPO sequences in order to determine the location of the mutation.

[0076] In one embodiment, a method according to the invention is provided, wherein the PPO-resistant weeds to be controlled are selected from the group consisting of Amaranthus tricolor (Asian Amaranthus tricolor), Amaranthus viridiflorus (Synonym: quitensis) (Smooth Pigweed), Palmer Amaranth, Amaranthus retroflexus (Redroot Pigweed), Amaranthus scabra (Western Amaranth) (Tall / Common Water Hemp), Common Ragweed (Common Ragweed), Avena sativa (Wild Oats), Sumatran Fleabane, Flixweed, Goosegrass (Cricket Grass), Poinsettia leucophylla (Wild Poinsettia), Rigid Ryegrass, Poa annua (Annual Bluegrass) and Senecio vernalis (Eastern Groundsel).

[0077] Preferably, the PPO-resistant weeds to be controlled are selected from Amaranthus viridis (synonym: quitensis) (Smooth Pigweed), Palmer Amaranth, Amaranthus retroflexus (Redroot Pigweed) and Amaranthus scabra (Western Amaranth) (Tall / Common Waterhemp).

[0078] More preferably, the PPO-resistant weed to be controlled is Palmer Amaranth or Amaranthus striata (Western Amaranthus) (High / Common Water Hemp).

[0079] In one embodiment, the PPO-resistant weed has a AG210, G399A, or R128 mutation in the protoporphyrinogen oxidase enzyme that confers resistance to PPO-inhibiting herbicides.

[0080] In one embodiment, the PPO-resistant weed has a glycine amino acid in place of an arginine amino acid at codon 128 of PPX2L, ie, the PPO-resistant weed has an R128G mutation in the protoporphyrinogen oxidase enzyme that confers resistance to PPO-inhibiting herbicides.

[0081] In one embodiment, the PPO-resistant weed has a methionine amino acid in place of an arginine amino acid at codon 128 of PPX2L, ie, the PPO-resistant weed has an R128M mutation in the protoporphyrinogen oxidase enzyme that confers resistance to PPO-inhibiting herbicides.

[0082] In one embodiment, the PPO-resistant weed has a leucine amino acid in place of an arginine amino acid at codon 128 of PPX2L, ie, the PPO-resistant weed has an R128L mutation in the protoporphyrinogen oxidase enzyme that confers resistance to PPO-inhibiting herbicides.

[0083] In one embodiment, the PPO-resistant weed has a codon deletion in PPX2L at position 210. Preferably, the deleted codon is for the amino acid glycine.

[0084] In another embodiment, Palmer Amaranth and / or Amaranthus sclerosus has a glycine amino acid at codon 128 in the gene encoding the porphyrinogen oxidase enzyme. Preferably, Palmer Amaranth and / or Amaranthus sclerosus has a glycine amino acid at codon 128 of PPX2L. More preferably, Palmer Amaranth and / or Amaranthus sclerosus has a glycine amino acid instead of an arginine amino acid at codon 128 of PPX2L.

[0085] In another embodiment, Palmer Amaranth and / or Amaranthus sclerosus has a methionine amino acid at codon 128 in the gene encoding the porphyrinogen oxidase enzyme. Preferably, Palmer Amaranth and / or Amaranthus sclerosus has a methionine amino acid at codon 128 of PPX2L. More preferably, Palmer Amaranth and / or Amaranthus sclerosus has a methionine amino acid instead of an arginine amino acid at codon 128 of PPX2L.

[0086] 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 of PPX2L. More preferably, the deleted codon is for the amino acid glycine.

[0087] In another embodiment, Amaranthus palmeri and / or Amaranthus sclerosus have a codon deletion at position 210 in the gene encoding the porphyrinogen oxidase enzyme. Preferably, Amaranthus palmeri and / or Amaranthus sclerosus have a codon deletion at position 210 of PPX2L. More preferably, Amaranthus palmeri and / or Amaranthus sclerosus have a glycine amino acid deletion.

[0088] In another embodiment, the weed has an alanine amino acid at codon 399 in 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 instead of a glycine amino acid at codon 399 of PPO2.

[0089] In another embodiment, Palmer Amaranth and / or Amaranthus sclerosus has an alanine amino acid at codon 399 in the gene encoding the porphyrinogen oxidase enzyme. Preferably, Palmer Amaranth and / or Amaranthus sclerosus has an alanine amino acid at codon 399 of PPO2. More preferably, Palmer Amaranth and / or Amaranthus sclerosus has an alanine amino acid instead of a glycine amino acid at codon 399 of PPO2.

[0090] The weeds may be selected from the group consisting of: Amaranthus species, Amaranthus species, Ambrosia species, Avena species, Ligusticum species, Descurainia species, Euphorbia species and Senecio species. Preferably, the weeds are Amaranthus species. More preferably, the weeds are Palmer amaranth and / or Amaranthus scabra.

[0091] Weeds of the present application are to be understood to also include those 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, by conventional breeding methods or by genetic engineering. Examples include Palmer amaranth that has evolved resistance to glyphosate and / or acetolactate synthase (ALS) inhibiting herbicides.

[0092] The present invention further provides a method for selectively controlling weeds in a location comprising useful (crop) plants and weeds, wherein the method comprises applying to the location a weed-controlling amount of a compound of formula (I) according to the present invention. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. It should be noted that the compounds of formula (I) show greatly improved selectivity compared to known structurally similar compounds. 'Location' means the area in which the plant is growing or will grow. Application can be applied to the location before and / or after emergence of the crop plant. Some crop plants can inherently tolerate the herbicidal action of the compound of formula (I). In the context of the present invention, target crops and / or useful plants to be protected typically include perennial and annual crops, such as berry plants, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar beets and fodder beets, coffee beans, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apples, apricots, avocados, bananas, cherries, citrus, nectarines, peaches, pears and plums; grasses, for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and zoysia grass; herbs such as basil, borage, chives, cilantro, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palm plants such as oil palms; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa trees, coconut trees, olive trees and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melons, okra, onions, peppers, potatoes, pumpkins, rhubarb, spinach and tomatoes; and grapevines such as 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 crops and nursery crops, including flower gardening.

[0093] The application rate of the compound of formula I can vary within wide limits and depends on the nature of the soil, the application method (pre-emergence or post-emergence; seed dressing; application to seed furrows; no-till application, etc.), crop plants, one or more weeds to be controlled, the climatic conditions at the time and other factors governed by the application method, application time and target crop. The compound of formula I according to the present invention is usually applied at a rate of from 10g / ha to 1000g / ha, especially from 25g / ha to 500g / ha, more especially from 50g / ha to 250g / ha, even more especially from 50g / ha to 200g / ha. In a particularly preferred embodiment, the compound of formula (I) according to the present invention is usually applied at a rate of from 100g / ha to 200g / ha.

[0094] Application is usually carried out by spraying the composition, typically by means of a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or drenching may also be used.

[0095] The term "useful plants" is to be understood as also including useful plants which have been rendered tolerant to herbicides such as bromoxynil or classes of herbicides such as, for example, 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, ALS inhibitors such as primisulfuron, primisulfuron and trifloxysulfuron, (5-enol-pyruvyl-shikimate-3-phosphate-synthetase) (EPSPS) inhibitors, glutamine synthetase (GS) inhibitors or protoporphyrinogen oxidase (PPO) inhibitors as a result of conventional breeding methods or genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones such as imazamox by conventional breeding methods (mutagenesis) are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides or herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties, which are based on and Commercially available under the trade name ANTIQUID®.

[0096] The term "useful plants" is to be understood as also including useful plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0097] Examples of such plants are: (corn variety expressing CryIA(b) toxin); YieldGard (corn variety expressing CryIIIB(b1) toxin); YieldGard (maize varieties expressing CryIA(b) and CryIIIB(b1) toxins); (corn varieties expressing Cry9(c) toxin); (corn varieties expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confer tolerance to the herbicide glufosinate ammonium); (cotton variety, expressing CryIA(c) toxin); (cotton variety, expressing CryIA(c) toxin); (cotton varieties expressing CryIA (c) and CryIIA (b) toxins); (cotton varieties expressing VIP toxin); (potato variety, expressing CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait), RW (corn rootworm trait) and

[0098] The compound of formula (I) can be used in an unmodified form, or preferably, together with adjuvants conventionally used in the field of formulations, to provide a herbicidal composition. Therefore, the present invention further provides a herbicidal composition comprising at least one compound of formula (I) and an agriculturally acceptable carrier and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art.

[0099] For this purpose, the compound of formula (I) can be conveniently formulated as emulsifiable concentrates, pastes that can be coated, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also capsules (e.g. in polymeric substances) in a known manner. For the type of composition, the application method is selected according to the intended purpose and the environment at that time, such as spraying, atomizing, dusting, sowing, smearing or watering. The composition can also contain other adjuvants, such as stabilizers, defoamers, viscosity modifiers, adhesives or tackifiers, together with fertilizers, micronutrient donors or other preparations for obtaining special effects.

[0100] Suitable carriers and adjuvants, for example for agricultural use, can be solid or liquid and are substances useful in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, adhesives or fertilizers. Such carriers are for example described in WO 97 / 33890.

[0101] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations contain anti-settling agents and dispersants, and may further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. When used, these concentrates are diluted in water and usually applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0102] Wettable powders are in the form of finely divided particles that disperse easily in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include Fuller's earth, kaolin, silica and other easily wetted organic or inorganic solids. Wettable powders usually contain from 5% to 95% of the active ingredient plus a small amount of a wetting agent, dispersant or emulsifier.

[0103] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids and may consist entirely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquids and are 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.

[0104] Granular formulations include both extrudates and coarser granules and are usually applied undiluted to the area to be treated. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials that absorb or can be coated with active compounds. Granular formulations usually contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic volatile oils, kerosene and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrins, glues or synthetic resins.

[0105] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

[0106] Microcapsules are typically droplets or particles of active ingredients encapsulated in an inert porous shell that allows the encapsulated material to escape into the environment at a controlled rate. The diameter of the encapsulated droplets is typically 1 to 50 microns. The encapsulated liquid typically accounts for 50% to 95% of the weight of the capsule and can also contain solvents in addition to the active compound. The encapsulated particles are usually porous particles, in which the porous membrane seals the particle pores and retains the active species in the form of a liquid inside the particle pores. The diameter of the particles typically ranges from 1 mm to 1 cm and preferably 1 mm to 2 mm. The particles are formed by extrusion, coagulation or spheroidization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbon fine particles. Shell or membrane materials include natural and synthetic rubbers, fiber materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0107] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent (such as acetone, alkylated naphthalenes, xylene and other organic solvents) in which the active ingredient is completely soluble at the desired concentration. Pressurized sprays may also be used in which the active ingredient is dispersed in finely divided form due to evaporation of a low-boiling dispersant solvent carrier.

[0108] Suitable agricultural adjuvants and carriers useful for formulating the compositions of the present invention in the above-mentioned formulation types are well known to those of ordinary skill in the art.

[0109] The liquid carriers that can be used include, for example, water, toluene, xylene, naphtha, 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 rosin acid ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide ... amide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate, glycerol monoethyl Acid esters, triacetin, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, poly Ethylene 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, glycerol and N-methyl-2-pyrrolidone. Water is generally the carrier of choice for diluting concentrates.

[0110] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

[0111] A wide range of surfactants may be advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These agents, when used, generally comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be employed as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products such as nonylphenol-C 18 Ethoxylates; alcohol-alkylene oxide addition products, such as tridecanol-C 16Ethoxylates; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; salts of dialkyl sulfosuccinates such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters such as sorbitan oleate; quaternary amines such as lauryltrimethylammonium 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 phosphates.

[0112] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, opacifiers, compatibilizing agents, defoamers, masking agents, neutralizing and buffering agents, corrosion inhibitors, dyes, flavor enhancers, spreading agents, penetration aids, micronutrients, emollients, lubricants, and fixatives.

[0113] Compounds with formula (I) are usually used in the form of agricultural chemical compositions and can be applied to crop areas or pending crops simultaneously or sequentially with other compounds. For example, these other compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, together with several mixtures in insecticides, fungicides, bactericides, nematicides, molluscicides or these preparations, if desired together with other carriers, surfactants or the adjuvants that promote application that are commonly used in the formulation field. In addition, herbicidal compounds of the present invention can also be used in combination with one or more other herbicides and / or plant growth regulators.

[0114] Examples

[0115] The following examples are used to illustrate the present invention.

[0116] Preparation Examples

[0117]

[0118] The active ingredient is mixed thoroughly with the adjuvant and the mixture is ground thoroughly in a suitable grinder to provide a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0119]

[0120] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to provide a dust that can be used directly for seed treatment.

[0121] Emulsifiable concentrates

[0122]

[0123] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0124]

[0125] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0126] Extruder Granules

[0127]

[0128] The active ingredient is mixed with the auxiliary and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0129] Coated granules

[0130] Active ingredient [compound of formula (I)] 8%

[0131] Polyethylene glycol (molecular weight 200) 3%

[0132] Kaolin 89%

[0133] The finely ground active ingredient is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0134] Suspension concentrates

[0135]

[0136] The finely ground active ingredients are intimately mixed with adjuvants to give suspension concentrates from which suspension concentrates of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against infection by microorganisms by spraying, pouring or immersion.

[0137] Flowable concentrate for seed treatment

[0138]

[0139] The finely ground active ingredients are intimately mixed with adjuvants to give suspension concentrates from which suspension concentrates of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against infection by microorganisms by spraying, pouring or immersion.

[0140] Extended-release capsule suspension

[0141] 28 parts of the combination of compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This 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 reached. To this emulsion is added a mixture of 2.8 parts of 1,6-hexanediamine in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete.

[0142] The obtained capsule suspension was stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contained 28% of active ingredient. The diameter of the medium capsule was 8-15 microns.

[0143] The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose.

[0144] Biological Examples

[0145] Example 1: Control of plants with a mutation at codon 128 by post-emergence application of a PPO herbicide

[0146] The commercial standard PPO inhibitor fomesafen and compound 8 of the present application were applied to three Palmer amaranth populations to determine the effect of mutating the wild-type arginine at codon 128 in PPX2L to glycine or methionine.

[0147] Three populations of Palmer amaranth were used: a population known to be sensitive to a PPO inhibitor ('sensitive'), a population in which every individual was known to be homozygous for glycine at codon 128 in the protoporphyrinogen oxidase gene PPX2L ('128G'), and a population in which every individual was known to be homozygous for methionine at codon 128 in the protoporphyrinogen oxidase gene PPX2L ('128M').

[0148] Seeds were sown in seed trays containing Ericaceous compost and covered with vermiculite. When the height was approximately 1 inch, plants were transplanted 1 per pot into 3-inch diameter pots containing Ericaceous compost. Pots were watered and maintained in a greenhouse, providing 16H 180 μmol m -2 s -1 A photoperiod of 100°C, a temperature of 24°C during the day and 18°C ​​at night, and a relative humidity of 65% until 3 inches high, at which time the herbicide was applied at the use rates specified in Table 1 below to 14 individual plants at each rate for each biotype.

[0149] All treatments were used as commercial adjuvants in reverse osmosis water at 0.5% by volume Compound 8 was initially dissolved as a 5% solution in a solvent mixture containing 11.12% Emulsogen EL 360, 44.44% Dowanol DPM and 44.44% N-methylpyrrolidone before dilution with water. Herbicide application was carried out in a track sprayer with a flat fan nozzle at 200 L / ha. -1 Apply herbicide treatments at a rate of .

[0150] After treatment, plants were watered and maintained in a greenhouse, providing 16H 180 μmol m -2 s -1 The plants were maintained at a photoperiod of 1 20°C, a temperature of 24°C during the day and 18°C ​​at night, and a relative humidity of 65% until 14 days after application, at which time they were evaluated on a 'dead or alive' basis. Plants still alive at this time were classified as surviving the herbicide application, and the average results of this evaluation are presented in Table 1.

[0151] Table 1

[0152]

[0153] in conclusion

[0154] Compound 8 demonstrated similar control of 'sensitive' populations as fomesafen, with both herbicides showing similar activity at 8 g ai / ha. -1 Complete control of this population (i.e., no surviving plants) was achieved at the application rate of 16 g ai / ha. However, unexpectedly, compound 8 demonstrated -1 The ability to achieve full control of both '128G' and '128M' at a rate of 1.5 g ai / ha, while fomesafen was only able to achieve full control of both '128G' and '128M' at 1.5 g ai / ha -1 Full control of '128M' is achieved at a rate of 128g ai / ha -1 Only 5 / 14 of the '128G' instances can be killed at a rate of

[0155] Example 2: Control of plants with a mutation at codon 210 by post-emergence application of a PPO herbicide

[0156] The commercial standard PPO inhibitor fomesafen and the compound 8 of the present application were applied to a population of Amaranthus sclerotiorum resistant to the PPO inhibitor herbicide. In particular, it is known that each individual plant in the population of Amaranthus sclerotiorum is homozygous for a deletion of the glycine residue at codon 210 in the protoporphyrinogen oxidase gene PPX2L.

[0157] Seeds were sown in seed trays containing Ericaceous compost and covered with vermiculite. When the height was approximately 1 inch, plants were transplanted 1 per pot into 3-inch diameter pots containing Ericaceous compost. Pots were watered and maintained in a greenhouse, providing 16H 180 μmol m -2 s -1 A photoperiod of 100°C, a temperature of 24°C during the day and 18°C ​​at night, and a relative humidity of 65% until 3 inches high, at which time the herbicide was applied at the use rates specified in Table 2 below to 16 individual plants at each rate.

[0158] All treatments were used as commercial adjuvants in reverse osmosis water at 1% by volume Compound 8 was initially dissolved as a 5% solution in a solvent mixture containing 11.12% Emulsogen EL 360, 44.44% Dowanol DPM and 44.44% N-methylpyrrolidone before dilution with water. Herbicide application was carried out in a track sprayer with a flat fan nozzle at 200 L / ha. -1 Apply herbicide treatments at a rate of .

[0159] After treatment, plants were watered and maintained in a greenhouse, providing 16H 180 μmol m -2 s -1 The plants were maintained at a photoperiod of 10°C, a temperature of 24°C during the day and 18°C ​​at night, and a relative humidity of 65% until 14 days after application, at which time they were evaluated on a 'dead or alive' basis. Plants still alive at this time were classified as surviving the herbicide application, and the average results of this evaluation are presented in Table 2.

[0160] Table 2

[0161]

[0162] in conclusion

[0163] Unexpectedly, Compound 8 demonstrated superior control of Amaranthus scabra with a mutation at codon 210 that is resistant to PPO inhibitor herbicides compared to fomesafen, especially at use rates of at least 8-105 g / ha. In particular, Compound 8 demonstrated superior control of Amaranthus scabra with a mutation at codon 210 that is resistant to PPO inhibitor herbicides compared to fomesafen, especially at use rates of at least 8-105 g / ha. -1 When applied, no plants survived. In contrast, fomesafen was applied at equal to or greater than 210 gai / ha -1 At the time of application, no plants survived.

[0164] Example 3: Control of plants with mutations at codon 210 by PPO herbicides in field trials

[0165] Field trials were conducted in small plots of Amaranthus sutchuenensis in Illinois, USA, where approximately 60%-70% of the Amaranthus sutchuenensis plants contained the ΔG210 mutation.

[0166] The experiment was arranged as a randomized complete block design with two replicates per treatment. The plot size of each replicate was set at 10m 2 . Compound 8 and commercial standard PPO herbicides (safensulfuron, fomesafen, glyphosate, glufosinate and fluazifop-butyl) were applied to Amaranthus scabra at a height of about 4 inches (about 10 cm) using a volume of water of 300 l / ha. After 14 days of application, the efficacy of the tested compounds was visually assessed and expressed as % weed control, with the rating ranging from 100% being complete control and 0% indicating weed population / growth similar to that observed in the untreated check. For reliability of the ratings, only species present in sufficient density and consistency were assessed. The results are presented in Table 3.

[0167] Table 3: Control of Amaranthus scabra as assessed visually as % weed control 14 days after application.

[0168]

[0169] in conclusion

[0170] Example 3 demonstrates that compound 8 provides excellent weed control of Amaranthus scabra against PPO inhibitor herbicides at all tested rates of 50 to 200 g AI / ha. The efficacy at use rates of 100 to 200 g AI / ha was particularly strong (>90%). Surprisingly, compound 8 was significantly superior to all standard commercial products (including saflufenacil, fomesafen, glyphosate, glufosinate and fluazifop-butyl) at all tested rates between 50 and 200 g AI / ha.

Claims

1. A method for controlling the growth of weeds that are resistant to porphyrinogen IX oxidase (PPO) inhibitor herbicides, the method comprising applying to the weeds, a portion of the weeds, weed propagation material, or the locus of the weeds an effective amount of a compound having the formula (I): in R 1 and R 2 each selected from the group consisting of: hydrogen and halogen; R 3 Selected from the group consisting of: hydrogen, C1-C4 alkyl, CO2R 5 and CH2OR 6 ; R 4 selected from the group consisting of: hydrogen and C1-C4 alkyl; R 5 Selected from the group consisting of: hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, C1-C4 alkoxy, C1-C4 alkyl, C 1-4 Alkylcarbonyl C 1-4 Alkyl and heterocyclic C1-C3 alkyl; R 6 Selected from the group consisting of C1-C2 alkylsulfonyl, C1-C4 alkylcarbonyl and C3-C4 cycloalkylcarbonyl; R 7 Selected from the group consisting of: hydrogen, C1-C4 alkyl and C1-C4 haloalkyl; R 8 is selected from the group consisting of: hydrogen, amino, C1-C6 alkyl, C3-C6 alkenyl, and C3-C6 alkynyl; and Among the PPO-resistant weeds are weeds resistant to at least one PPO-inhibiting herbicide other than the compound of formula (I).

2. The method according to claim 1, wherein: These PPO-resistant weeds have mutations at amino acid 128 and / or amino acid 210 in the gene encoding the protoporphyrinogen oxidase enzyme.

3. The method according to claim 1 or 2, wherein: These PPO-resistant weeds have a glycine amino acid at codon 128 in the gene encoding the protoporphyrinogen oxidase enzyme.

4. The method according to claim 1 or 2, wherein: These PPO-resistant weeds have the amino acid methionine at codon 128 in the gene encoding the protoporphyrinogen oxidase enzyme.

5. The method according to claim 1 or 2, wherein: These PPO-resistant weeds have a codon deletion at position 210 in the gene encoding the protoporphyrinogen oxidase enzyme.

6. The method according to claim 5, wherein: The deleted codon is for the amino acid glycine.

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

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

9. The method according to any one of claims 1 to 6, wherein: The PPO-resistant weeds are selected from the group consisting of Palmer amaranth and Amaranthus scabra.

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 which comprises at least one further compound: the herbicide B.

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

12. The 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. Use of a compound of formula (I) as defined in claim 1 for controlling the growth of weeds that are resistant to porphyrinogen IX oxidase (PPO) inhibitor herbicides.

15. The use according to claim 14, wherein These weeds that are resistant to porphyrinogen IX oxidase (PPO) inhibitor herbicides have mutations at amino acid 128 and / or amino acid 210 in the gene encoding the protoporphyrinogen oxidase enzyme.

16. Use of a composition as defined in any one of claims 10 to 12 for controlling the growth of weeds that are resistant to porphyrinogen IX oxidase (PPO) inhibitor herbicides.

17. The use according to claim 16, wherein These weeds that are resistant to porphyrinogen IX oxidase (PPO) inhibitor herbicides have mutations at amino acid 128 and / or amino acid 210 in the gene encoding the protoporphyrinogen oxidase enzyme.

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