Herbicide / safener combinations based on seed treatment using substituted [(1, 5-diphenyl-1h-1, 2, 4-triazol-3-yl) oxy] acetic acid and salt safeners thereof

Abstract

The present invention relates to a novel method for reducing crop damage, comprising the seed treatment application of a safener followed by pre-emergence or post-emergence treatment using a substituted isoxazoline carboxamide having a herbicidal effect.

Description

[0001] This invention relates to a novel method for preventing crop damage, comprising seed treatment of crop seeds with a safener compound based on a substituted [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid or an agriculturally chemically acceptable salt thereof, followed by application of a herbicidal compound based on a substituted isoxazoline carboxamide or an agriculturally chemically acceptable salt thereof. The combination of seed-treated crops and post-sowing herbicidal treatment enables highly selective control of weeds in a variety of beneficial plant crops.

[0002] Substituted isoxazoline formamides are known as effective herbicides by WO2018 / 228985 and WO2019 / 145245. However, the activity of these compounds and / or their compatibility with crop plants is not entirely satisfactory under all conditions, and therefore the use of different safeners has been considered, for example, as described in WO2021 / 245003, WO2021 / 245004, WO2021 / 245005, WO2021 / 245006, WO2021 / 245007, WO2021 / 245008 and WO2021 / 245009.

[0003] Substituted [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid and its salts are a new class of safeners first described in WO2021 / 105101. Combinations of substituted [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid with different classes of herbicides are further described in WO2022 / 238194.

[0004] Although various solutions have been proposed in the prior art to protect crops from the herbicidal activity of substituted isoxazoline formamide, further improvements in protection methods are needed to reduce the degree of crop damage.

[0005] Surprisingly, it has now been found that crop seeds treated with substituted [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid and its salts can be effectively combined with herbicide treatments using certain substituted isoxazoline carboxamides. This seed treatment provides high protection for the crop, greatly preventing crop damage, while maintaining high herbicidal activity against unwanted weeds.

[0006] Therefore, the present invention provides a method for reducing crop damage, comprising treating crop seeds with a safener compound of formula (II) before sowing.

[0007]

[0008] in

[0009] (R1' ) n' -Phenyl groups are represented by one of the groups from Q-1.1 to Q-1.55.

[0010]

[0011]

[0012] Furthermore, (R) 2' ) m' -The phenyl group is selected from one of the groups Q-2.1 to Q-2.55.

[0013]

[0014]

[0015] R 3' It is hydrogen.

[0016] and

[0017] R 4'The following are the compounds: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, phenyl, benzyl, CH2(4-Cl-Ph), CH2(4-F-Ph), CH2(4-OMe-Ph), 2-methoxyethyl, tetrahydrofuran-2-ylmethyl, tetrahydrofuran-3-ylmethyl, tetrahydropyran-2-ylmethyl, tetrahydropyran-3-yl-methyl, tetrahydropyran-4-yl-methyl, methylpropionate-3-yl, ethylpropionate-3-yl, methylacetate-2-yl -yl, ethyl acetate-2-yl, methyl neopentanoate-2-yl, ethyl neopentanoate-3-yl, methyl-2-methylpropionate-3-yl, methyl-2,2-dimethylpropionate-3-yl, ethyl-2-methylpropionate-3-yl, methyl-2-propionate-2-yl, ethyl-2-propionate-2-yl, methyl acetate-2-yl, ethyl acetate-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylate-2-yl, 2-(dimethylamino)ethyl, oxetane-3-yl, (3-methyloxetane-3-yl)methyl 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 2,2,3,3,3-pentafluoropropyl, cyclopropylmethyl, 1-cyclopropyl-ethyl, (1-methyl-cyclopropyl)-methyl, (2,2-dichlorocyclopropyl)-methyl, (2,2-dimethyl-cyclopropyl)-methyl, allyl, propyne (prop-2-yn-1-yl), 2-chloroprop-2-en-1-yl, 3-phenylprop-2-yn-1-yl, 3,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-fluoroprop-2-en-1-yl, methylprop-2-yn-1-yl, 2-methylprop- 2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, but-2-yn-1-yl, but-3-yn-1-yl, 4-chlorobut-2-yn-1-yl, 3-methyl-but-2-en-1-yl, 3-methyl-but-1-en-1-yl, 1-(2e)-1-methyl-but-2-en-1-yl, (e)-pent-3-en-2-yl or (z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, hept-2-yl, isobutyl, 1,3-dioxolanecyclo-2-ylmethyl or 1-ethyl-5-methyl-1H-pyrazole-4-methyl;

[0018] Subsequently, a herbicide of formula (I) or its agrochemically acceptable salt is applied after sowing.

[0019]

[0020] in

[0021] G represents OR 4 or NR7 R 8 ;

[0022] R 1 and R 2 Each represents hydrogen;

[0023] R 3 The term represents (C1-C5)-alkyl, (C3-C6)-cycloalkyl, (C2-C5)-alkenyl, (C2-C5)-alkynyl, or (C1-C5)-alkoxy, each of which is optionally substituted m times by a substituent selected from halogen, cyano, (C1-C5)-alkoxy, and hydroxyl.

[0024] R 4 It represents hydrogen.

[0025] Or it can mean (C1-C) 12 (C3-C7)-alkyl, (C3-C7)-cycloalkyl-(C1-C8)-alkyl, (C2-C8)-alkenyl, (C5-C6)-cycloalkenyl, (C1-C4)-alkylphenyl, or (C2-C8)-ynyl, each optionally selected from halogen, cyano, (C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl, hydroxyl, S(O) n R 5 The substituents are replaced "m" times:

[0026] R 5 The designation represents (C1-C8)-alkyl, (C2-C8)-alkenyl, (C3-C6)-cycloalkyl, benzyl, CON((C1-C3)-alkyl)2 or (C1-C8)-alkyl-C(O)-(C1-C8)-alkyl, each of which is optionally substituted m times by a substituent selected from halogens and cyano groups;

[0027] R 6 It represents hydrogen.

[0028] or

[0029] The group represents (C1-C8)-alkyl, (C3-C6)-cycloalkyl, (C3-C8)-alkenyl or (C3-C8)-ynyl, each of which is optionally substituted m times by a substituent selected from halogen, cyano and (C1-C2)alkoxy.

[0030] R 7 R 8 Each of these can be independently represented as hydrogen, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkyl, N((C1-C3)-alkyl)2, or S(O). n R 5 ,

[0031] or

[0032] R 7 and R 8 Together with the nitrogen atoms they are attached to, they form saturated, partially unsaturated, or fully unsaturated five-, six-, or seven-membered rings. These rings, in addition to nitrogen atoms, may contain "r" carbon atoms and "o" oxygen atoms, and are optionally selected from halogens, (C1-C6)-alkyl groups, halo-(C1-C6)-alkyl groups, oxo groups, and CO2R groups. 6 The substituents are replaced "m" times;

[0033] Z represents a residue selected from any one of Z-1 to Z-8:

[0034]

[0035] The arrows indicate the bonds that connect to the CO-G group in formula (I);

[0036] X 2 X 4 and X 6 They can represent hydrogen or fluorine independently;

[0037] X 3 and X 5 Each can be represented independently as hydrogen, chlorine, cyanide, or fluorine;

[0038] or

[0039] The terms (C1-C3)-alkyl and (C1-C3)-alkoxy are indicated, each of which is optionally substituted m times by a substituent selected from fluorine or chlorine.

[0040] m represents 0, 1, 2, 3, 4 or 5;

[0041] n represents 0, 1, or 2;

[0042] o represents 0, 1, or 2;

[0043] r represents 3, 4, 5, or 6.

[0044] Preferably, the compound of formula (I) is a compound of formula (Ia) or an agriculturally chemically acceptable salt thereof.

[0045]

[0046] in

[0047] X 3 X 5 R 3 And G as described above;

[0048] Z represents Z-1a, Z-1b, Z-2a, Z-3a, Z-4a, Z-5a, Z-6a, Z-7a or Z-8a,

[0049]

[0050] Z-4a represents a mixture of the two structures Z-4b and Z-4c.

[0051] ;

[0052] Furthermore, Z-8a represents a mixture of the Z-8b and Z-8c structures.

[0053] ;

[0054] Furthermore, the arrows indicate the bonds that connect to the CO-G group in formula (Ia).

[0055] More preferably, the compound of formula (Ia) is selected from the compounds in Table 1 below or their agriculturally chemically acceptable salts.

[0056]

[0057] (Ia)

[0058] Table 1: Examples of compounds of formula (Ia)

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067] The compounds of formula (I) are known from WO2018 / 228985 and WO2019 / 145245 and can be synthesized according to the methods described therein.

[0068] Even more preferably, the compounds of formula (I) are selected from...

[0069] methyl rel-(2R,4R)-4-[[3-(3,5-dichlorophenyl)-5-methoxy-4H-isoxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylate,

[0070] methyl rel-(2R,4R)-4-[[3-(3,5-dichlorophenyl)-5-vinyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylate,

[0071] (2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid methyl ester,

[0072] rel-(2R,4R)-4-[[3-(3-fluorophenyl)-5-methyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid isopropyl ester,

[0073] (3R)-3-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazol-5-carbonyl]amino]-2,3-dihydrofuran-5-carboxylic acid methyl ester, and

[0074] (3R)-3-[[(5R)-3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]-2,3-dihydrofuran-5-carboxylic acid methyl ester.

[0075] In another embodiment, the compound of formula (II) is selected from...

[0076] Methyl-{[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate,

[0077] {[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid,

[0078] Methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate,

[0079] {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid,

[0080] Methyl-{[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate,

[0081] {[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid,

[0082] Methyl-{[5-(4-bromo-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate,

[0083] {[5-(4-bromo-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid,

[0084] Methoxyethyl-{[1-(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, and

[0085] {[1-(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid.

[0086] These preferred compounds of formula (II) are described in Table 2 below.

[0087] Table 2: Preferred examples of compounds of formula (II)

[0088]

[0089]

[0090]

[0091] For example, WO2021 / 105101 describes compounds of this formula (II) and can be synthesized according to the methods described therein.

[0092] In the context of this invention, particularly preferred safety agent compounds of formula (II) are compounds A1, A3, A5, A7 and A9 in Table 2 above.

[0093] In another embodiment, the herbicide compound of formula (I) is...

[0094] (2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid methyl ester;

[0095] Furthermore, the safety compound of formula (II) is selected from...

[0096] Methyl-{[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate,

[0097] Methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate,

[0098] Methyl-{[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate,

[0099] Methyl-{[5-(4-bromo-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, and

[0100] Methoxyethyl-{[1-(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate.

[0101] In another embodiment, the herbicide compound of formula (I) is...

[0102] (2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylate; and the safety compound of formula (II) is methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate.

[0103] In another embodiment, the herbicidal compound of formula (I) is applied during the pre-emergence treatment.

[0104] In another embodiment, in the post-emergence treatment, the herbicidal compound of formula (I) is preferably applied in the early or mid-post-emergence treatment.

[0105] In another implementation, the crop is a genetically modified plant.

[0106] In another embodiment, the safener compound (II) is applied to the seeds at an application rate of 0.01 to 2 g / kg of seeds, preferably 0.1 to 1 g / kg of seeds, more preferably 0.2 to 0.8 g / kg of seeds, and even more preferably 0.2 to 0.5 g / kg of seeds.

[0107] In another embodiment, the herbicidal compound of formula (I) is applied at the following application rate: 0.1 to 1000 g / ha, preferably 0.5 to 500 g / ha, more preferably 0.7 to 100 g / ha, and even more preferably 1 to 50 g / ha.

[0108] In another embodiment, the method further includes applying the safener compound of formula (II) after sowing, either pre-emergence or post-emergence. Preferably, the safener compound of formula (II) is applied together with the herbicide compound of formula (I) in a tank mix. Preferably, the safener compound of formula (II) is applied together with the herbicide compound of formula (I) in a tank mix at a rate of 1 to 1000 g / ha, preferably 5 to 500 g / ha, more preferably 10 to 100 g / ha, and even more preferably 25 to 75 g / ha.

[0109] The safety effect is further enhanced by this dual application of the safener compound, namely during seed treatment and (after sowing) before or after emergence.

[0110] definition

[0111] halogen Groups representing fluorine, chlorine, bromine, and iodine. Groups representing fluorine and chlorine are preferred.

[0112] alkyl This indicates a saturated straight-chain or branched hydrocarbon group, which in each case has a specified number of carbon atoms, such as C1-C6-alkyl, including methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, etc. 1-Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl.

[0113] alkenylThis indicates an unsaturated straight-chain or branched hydrocarbon group, which in each case has a specified number of carbon atoms and a double bond in any position, such as C2-C6-alkenyl, including vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2- Butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- Pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Ethyl-1-methyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl and 1-Ethyl-2-methyl-2-propenyl.

[0114] acetylinThis refers to a straight-chain or branched hydrocarbon group having 2 to 8, preferably 2 to 6, carbon atoms and a triple bond at any position. Non-limiting examples include ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methylprop-2-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, 1-methylbut-2-ynyl, 1-methylbut-3-ynyl, 2-methylbut-3-ynyl, 3-methylbut-1-ynyl, 1,1-dimethylprop-2-ynyl, 1-ethylprop-2-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylpent-2-ynyl, 1-methyl The following are listed: 3-methylpentan-yne, 1-methylpentan-4-yne, 2-methylpentan-3-yne, 2-methylpentan-4-yne, 3-methylpentan-1-yne, 3-methylpentan-4-yne, 4-methylpentan-1-yne, 4-methylpentan-2-yne, 1,1-dimethylbutan-2-yne, 1,1-dimethylbutan-3-yne, 1,2-dimethylbutan-3-yne, 2,2-dimethylbutan-3-yne, 3,3-dimethylbutan-1-yne, 1-ethylbutan-2-yne, 1-ethylbutan-3-yne, 2-ethylbutan-3-yne, and 1-ethyl-1-methylpropan-2-yne.

[0115] cycloalkyl This indicates a preferred carbocyclic saturated ring system having 3-8 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. In the case of optionally substituted cycloalkyl groups, this includes ring systems with substituents, as well as substituents with double bonds on the cycloalkyl group, such as alkylene groups, like methylene groups.

[0116] AlkoxyThis indicates a saturated straight-chain or branched alkoxy group, which in each case has a specified number of carbon atoms, such as C1-C6-alkoxy groups, including methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, and 1,2-dimethylpropoxy. 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1,1-Dimethylbutoxy, 1,2-Dimethylbutoxy, 1,3-Dimethylbutoxy, 2,2-Dimethylbutoxy, 2,3-Dimethylbutoxy, 3,3-Dimethylbutoxy, 1-Ethylbutoxy, 2-Ethylbutoxy, 1,1,2-Trimethylpropoxy, 1,2,2-Trimethylpropoxy, 1-Ethyl-1-Methylpropoxy, and 1-Ethyl-2-Methylpropoxy. Halogen-substituted alkoxy groups refer to straight-chain or branched alkoxy groups, each having a specified number of carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by the halogen atoms specified above, such as C1-C2-haloalkoxy groups, including chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-1,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy.

[0117] Surprisingly, crop seeds treated with a safer compound of formula (II) have been found to be well protected from crop damage caused by the application of herbicides (i.e., substituted isoxazoline carboxamides of formula (I) and / or their salts).

[0118] Unexpectedly, when the substituted isoxazoline carboxamide of general formula (I) was used for herbicidal treatment, the compound of formula (II) was safer than other known safeners or antidotes (which are usually able to antagonize the damaging effects of herbicides on crop plants).

[0119] The emphasis here is on the particularly beneficial effect of treating crop seeds with compounds of formula (II) in protecting cereal crops such as wheat, barley, rye, corn, and rice.

[0120] The active compound complexes according to the invention can be used in combination with, for example, the following plants:

[0121] The following are dicotyledonous weeds:Genuses: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia ), Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

[0122] The following are dicotyledonous crops: Cotton (Gossypium), Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita, Helianthus.

[0123] The following monocotyledonous weedsGenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Bermuda grass The genera *ynodon*, *Monochoria*, *Fimbristylis*, *Sagittaria*, *Eleocharis*, *Scirpus*, *Paspalum*, *Ischaemum*, *Sphenoclea*, *Dactyloctenium*, *Agrostis*, *Alopecurus*, and *Apera*.

[0124] The following monocotyledonous crops : Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

[0125] However, the application of the active compounds of this invention is by no means limited to these genera, but is extended to other plants in the same manner. According to this invention, crop plants are all plants and plant varieties, including transgenic plants and plant varieties, where synergistic effects may also occur with transgenic plants and plant varieties.

[0126] In the context of this invention, the compositions, in addition to comprising the herbicidal compounds of formula (I) of this invention, also contain one or more other components, including but not limited to: formulation adjuvants, conventional additives for crop protection, and other compounds with agrochemical activity (e.g., fungicides and insecticides). Such compositions can also be used in the methods of this invention.

[0127] In another embodiment, the method of the present invention includes applying at least one other herbicide (c), wherein (c) is selected from a list including, but not limited to, the following herbicides:

[0128] Acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicabazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6 -(4-Chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, aminopyralid-dimethylammonium, aminopyralid-tripromine, amitrol, ammonium sulfamate, anilofos, asulam, asulam-potassium, asulam sodium Sodium), atrazine, azafenidin, azimsulfuron, beflubutamid, (S)-(-)-beflubutamid, beflubutamid-M, benzolin, benzolin-ethyl, benzolin-dimethylammonium, benzolin-potassium, benzfluralin, benzuresate, benzsulfuron, benzsulfuron-methyl, benzulide, bentazone, benzazol-sdium, benzobicyclon, benzofenap.Bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bipyrazone, bispyribac, bispyribac-sodium, bixlozone, bromacil, bromacil-lithium, bromacil-sodium, bromobutide, bromofenoxim, bromobutane Bromoxynil, bromoxynil-butyrate, bromoxynil-potassium, bromoxynil-heptanoate, bromoxynil-octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butyrazine, butyrazine Late, Cafenstrole, Cambendichlor, Carbetamide, Carfentrazone, Carfentrazone-ethyl, Chloramben, Chloramben-ammonium, Chloramben-diolamine, Chloramben-methyl, Chloramben-methylammonium, Chloramben-sodium, Chlorbromuron, Chlorfenac, Chlorfenac-ammonium, Chlorfenac-sodium, Chlorfenprop, Chlorfenprop-methyl, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl.Chlorophthalim, chlorotoluron, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, cinidon, cinidon-ethyl, cinmethylin, exo-(+)-cyhalothrin, i.e. (1R,2S,4S) )-4-isopropyl-1-methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptane, exo-(-)-cycloheptachlor (i.e., (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptane), cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-ethyl, clodinafop-methyl dinafop-propargyl), isoxaflutole (clomazone), clomeprop, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tripomine, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D (Including 2,4-D-ammonium, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-choline, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-D-diethanolamine, 2,4-D-doboxyl,2,4-D-Dodecylammonium, 2,4-D-2-Ethylhexyl ester (2,4-D-etexyl), 2,4-D-Ethyl ester (2,4-D-ethyl), 2-Ethylhexyl ester (2-ethylhexyl), 2,4-D-Heptylammonium, 2,4-D-Isobutyl ester, 2,4-D-Isooctyl ester, 2,4-D-Isopropyl ester, 2,4-D-Isopropylammonium, 2,4-D-Lithium, 2,4-D-Isooctyl ester, 2,4-D-Methyl ester, 2,4-D-Potassium, 2,4-D-Tetradodecylammonium, 2,4-D-Triethylammonium, 2,4-D-Triisopropanolammonium, 2,4-D-Triisopropanol (2,4-D-tripromine) and 2,4-D- Triethanolamine and its salts), 2,4-DB, 2,4-DB-butyl ester, 2,4-DB-dimethylammonium, 2,4-DB-isooctyl ester, 2,4-DB-potassium and 2,4-DB-sodium, daimuron (dymron), dalapon, dalapon calcium, dalapon-magnesium, dalapon-sodium, dazomet, dazomet-sodium, n-dedecyl alcohol, 7-deoxy-D-sedoheptulose, desmedipham, detosyl-pyrazolate (DTP), dicamba. And its salts, such as dicamba-biproamine, dicamba-N,N-bis(3-aminopropyl)methylamine, dicamba-butotyl, dicamba-choline, dicamba-diethylene glycolamine, dicamba-dimethylammonium, dicamba-diethanolaminemmonium, dicamba-diethylammonium, dicamba-isopropylammonium, dicamba-methyl ester, dicamba-monoethanolamine, and dicamba-olamine. ), dicamba-potassium, dicamba-sodium, dicamba-triethanolamine, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-butotyl, dichlorroprop-dimethylammonium, dichlororprop-etexyl2,4-Dichlorprop-ethylammonium, 2,4-Dichlorprop-isoctyl, 2,4-Dichlorprop-methyl, 2,4-Dichlorprop-postassium, 2,4-Dichlorprop-sodium, dichlorprop-P, dichlorprop-P-dimethylammonium, dichlorprop-2-ethylhexyl propionate rprop-P-etexyl), dichlorprop-P-potassium, dichlorprop-sodium, diclofop, diclofop-methyl, diclofop-P, diclofop-P-methyl, diclosulam, difenzoquat, difenzoquat-metilsulfate, diflufenican, diflufenzopyr, diflufenozide sodium opyr-sodium, dimefuron, dimepiperate, dimesulfazet, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, diinitramine, dinoterb, dinoterb-acetate, diphenamid, diquat, dibromodiflubenzuron (d) iquat-dibromid, diquat-dichloride, dithiopyr, diuron, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, endothal, endothal-diammonium, endothal-dipotassium, endothal-disodium, Epyrifenacil (S-3100)EPTC, esprocarb, ethafluralin, ethametsulfuron, ethametsulfuron-methyl, etiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-5231 (i.e., N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5- [Oxo-1H-tetrazol-1-yl]phenyl]-ethanesulfonamide), F-7967 (i.e., 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidin-2,4(1H,3H)-dione), fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenpyrazone, fenquinotrione, f-tetrazolyl sulfadiazine entrazamide, flamprop, flamprop-isoproyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, florpyrauxifen, florpyrauxifen-benzyl, fluazifop, fluazifop-butyl ), fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumicloracFlumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, flurenol-dimethylammonium, flurenol-methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, sodium tetrafluoropropionate, flupyrsulfuron n), flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, flusulfanilamide safen, fomesafen-sodium, foramsulfuron, foramsulfuron sodium salt, fosamine, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-sodium, L-glufosinate-ammonium, L-glufosiante-sodium, glufosi Glyphosate (P-sodium), glufosinate (P-ammonium), glyphosate, glyphosate-ammonium, glyphosate-isopropylammonium, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-potassium, glyphosate-sodium.Glyphosate-sesquisodium and glyphosate-trimesium, H-9201 (O-(2,4-dimethyl-6-nitrophenyl)-O-ethyl isopropylphosphoramidothioat), halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, and haloxyfop-ethoxyethyl. ethoxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, haloxifop-sodium, hexazinone, HNPC-A8169 (i.e., prop-2-yn-1-yl(2S)-2-{3-[(5-tert-butylpyridin-2-yl)oxy]phenoxy}propionate), HW-02 (i.e., 1-(dimethoxyphosphoryl)-ethyl-(2,4-dichlorophenoxy) Acetate), hydantocidin, imidazolic acid, methyl imidazolic acid, imazamethabenz, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, isopropylammonium, imidazoquinoline acid (imazaquin), imidazoquinoline ammonium, imidazoquinoline methyl ester, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methylIodosesulfuron-methyl-sodium, ioxynil, ioxynil-lithium, ioxynil-octanoate, ioxynil-potassium, and ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043 (i.e., 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole), ketospiradox, ketospiradox-potassium, lactoferrin, and cyclohexane. nacil), linuron, MCPA, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-2-ethylhexyl, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl MCPA-isopropylammonium, MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA-sodium, and MCPA-trolamine, MCPB, MCPB-methyl, MCPB-ethyl, and MCPB-sodium, 2-methyl-4-chloropropionic acid, 2-methyl-4-chloropropionic acid butoxyethyl ester, 2-methyl-4-chloropropionic acid dimethylamine, and 2-methyl-4-chloropropionic acid diethanolamine.2-Methyl-4-chloropropionic acid-(2-ethylhexyl) ester (mecoprop-etexyl), mecoprop-ethadyl, isooctyl 2-methyl-4-chloropropionic acid (mecoprop-isoctyl), methyl 2-methyl-4-chloropropionic acid (mecoprop-methyl), potassium 2-methyl-4-chloropropionic acid (mecoprop-potassium), sodium 2-methyl-4-chloropropionic acid (mecoprop-sodium), triethanolamine 2-methyl-4-chloropropionic acid (mecoprop-trolamine), purified 2-methyl-4-chloropropionic acid (mecoprop-P), purified 2-methyl-4-chloropropionic acid butoxyethyl ester (mecoprop-P-butotyl), purified 2-methyl-4- Mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, mefenacet, mefluidide, mefluidide-diolamine, mefluidide-potassium, mesosulfuron, mesosulfuron-methyl, and mesosulfuron sodium. Sodiumsalt, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, metiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, monosulfuron.Monosulfuron-methyl, MT-5950 (N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide), NGGC-011, napropamide, NC-310 (4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole), NC-656 (3-[isopropylsulfonyl)methyl]-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide), neburon, nicosulfuron, nonanoic acid (pelargonic acid) (acid), norflurazon, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, paraquat dichloride, paraquat-dimethylsulfate, pebulate, pendimethalin, penoxsulam, pentachlorphenol, pentoxazone, pethoxamid, petroleum oils), phenmedipham, phenmedipham-ethyl, picloram, picloram-dimethylammonium, picloram-etexyl (2-ethylhexyl) ester, picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium, picloram-triethylammonium, picloram-tripromine, picloram-trolamine.Picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, benzene Propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolyn ate (pyrazolate), pyrazosulfuron (pyrazosulfuron, pyrazosulfuron-ethyl), pyrazoxyfen (pyrazoxyfen), pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac (pyri... Minobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinclorac-dimethylammonium, quinclorac-methyl, quinmerac, quinoclamine, quizalofopQuizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, QYM201 (i.e., 1-{2-chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6-(trifluoromethyl)phenyl}piperidin-2-one), rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, and more. Simetryn, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYP-249 (i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate), SYP-300 (i.e., 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazine-6-yl]- 3-propyl-2-thioimidazolidine-4,5-dione), 2,3,6-TBA, TCA (trichloroacetic acid) and their salts, such as ammonium trichloroacetate, calcium trichloroacetate, ethyl trichloroacetate, magnesium trichloroacetate, sodium trichloroacetate, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, tetflupyrol imet, thaxtomin, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, toramezone, tralkoxydim, triafamone, tri-allateTriasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-choline, triclopyr-ethyl, triclopyr-triethylammonium, trietazine, trifloxysul furon, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, ureasulfate, vernolate, XDE-848, ZJ-0862 (i.e., 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline), 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-) Dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazol-5-carboxylic acid ethyl ester, 3-chloro-2-[3-(difluoromethyl)isoxazolyl-5-yl]phenyl-5-chloropyrimidin-2-yl ether, 2-(3,4-dimethoxyphenyl)-4-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-6-methylpyridazine-3(2H)-one, 2-({2-[(2-methoxyethoxy)methyl]-6-methylpyridin-3-yl}carbonyl)cyclohexane-1,3-dione, (5-hydroxy-1-methyl-1H-pyrazol-4-yl)(3,3,4-trimethyl-1,1-dioxo-2,3-dihydro-1-benzo[] Thiophene-5-yl) methyl ketone, 1-methyl-4-[(3,3,4-trimethyl-1,1-dioxy-2,3-dihydro-1-benzothiophene-5-yl)carbonyl]-1H-pyrazol-5-ylpropane-1-sulfonate, 4-{2-chloro-3-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-4-(methanesulfonyl)benzoyl}-1-methyl-1H-pyrazol-5-yl 1,3-dimethyl-1H-pyrazol-4-carboxylate, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid cyanomethyl ester, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid prop-2-ynyl ester,4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid benzyl ester, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid benzyl ester, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid benzyl ester, Ethyl H-indol-6-yl)pyridine-2-carboxylate, methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylate, methyl 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate, methyl 4-amino-3-chloro-6-[1-(2,2-dimethylpropionyl)-7- Methyl fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylate, methyl 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)-1H-indol-6-yl]pyridine-2-carboxylate, potassium 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate Sodium (indo-6-yl)pyridin-2-carboxylate, butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indo-6-yl)pyridin-2-carboxylate, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolin-2-one, 3-(5-tert-butyl-1,2-oxazol-3-yl)-4-hydroxy-1-methylimidazolin-2-one, abscisic acid acid), acibenzolar, acibenzolar-S-methyl, 1-aminocyclopropyl-1-methylcarboxylic acid and its derivatives, 5-aminolevolinic acid, ancymidol, 6-benzylaminopurine, brassinolide, brassinolide-ethyl, catechol, chitosan oligosaccharide (CO; the difference between CO and LCO is that they lack the dangling fatty acid chain characteristic of LCO. Chitosan oligosaccharide (CO) (sometimes also called N-acetylchitosan oligosaccharide) is also composed of GlcNAc residues, but it has the characteristics that distinguish them from chitin molecules [(C8H, 13 NO5) n [CAS No. 1398614] and chitosan molecules [(C5H 11 NO4) n[CAS No. 9012-76-4] side chain modification), chitin compounds, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propionic acid, daminozide, dazomet, sodium dazomet sodium, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, endothal-disodium, and endothal mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurenol-methyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic acid (acid) or its derivatives (e.g., methyl jasmonate), lipo-chitooligosaccharides (LCO, sometimes referred to as symbiotic nodule (Nod) signal (or Nod factor) or Myc factor), which consist of an oligosaccharide backbone having β-1,4-linked N-acetyl-D-glucosamine (“GlcNAc”) residues having N-linked fatty acyl chains condensed at non-reducing ends.As is known in the art, LCOs are distinguished by the number of GlcNAc residues in the backbone, the length and saturation of the fatty acyl chain, and the substitution of reducing and non-reducing sugar residues. Other components include linoleic acid or its derivatives, linolenic acid or its derivatives, maleic hydrazide, mepiquat chloride, mepiquat pentaborate, 1-methylcyclopropene, 3'-methylabscisic acid, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthoxyacetic acid, a mixture of nitrophenol salts, 4-oxo-4-[(2-phenylethyl)amino]butyric acid, paclobutrazol, 4-phenylbutyric acid, and N-phenylphthalamic acid. acid), prohexadione, prohexadione-calcium, prohydrojasmon, salicylic acid, methyl salicylate, strigolacton, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P, 2-fluoro-N-(3-methoxyphenyl)-9H-purine-6-amine.

[0129] "Pre-emergence" application refers to the application of herbicides to a target area (e.g., a cultivated field or region) before the plants have clearly emerged from the soil. "Post-emergence" application refers to the application of herbicides to a target area after the plants have clearly emerged from the soil. The terms "pre-emergence" and "post-emergence" can be defined using BBCH codes.

[0130] The BBCH code (familiar to those skilled in the art) provides information about the morphological developmental stages of plants. Officially, the abbreviation stands for the Federal Department of Biology, the Federal Register of Plant Varieties, and the Chemical Industry.

[0131] Pre-emergence (PE) = before seed germination or until BBCH stage 09.

[0132] Post-emergence (PO) = Apply to the aboveground parts of the plant; BBCH stage 10-31.

[0133] Early post-emergence stage = BBCH stage 10-12.

[0134] Mid-stage after emergence = BBCH stage 13-28.

[0135] Late post-emergence stage = BBCH stage 29-31.

[0136] The BBCH code can be used for both weed emergence and crop emergence. Preferably, the BBCH code refers to crop emergence. Example

[0137] A. Safety benefits of winter wheat

[0138] 1. Seed treatment of winter wheat (TRZAW)

[0139] For seed treatment, the safer compound A3 of the present invention (see Table 2 above) was used, along with the comparative safers mefenpyr-diethyl (CAS 135590-91-9) and cloquintocet-mexyl (CAS 99607-70-2).

[0140] After calculating the appropriate amounts of the required safener compounds (using WP and WG formulations), each safener is mixed with water in a drum. Water is used to ensure kernel distribution of the compounds on the seeds. Typically, the slurry volume (water + safener) is 800 ml / 100 kg of seeds. The seeds to be treated are placed in the mixing chamber of the seed treatment equipment. After the seeds are placed in the equipment, the slurry volume is introduced into the mixing chamber for 20 seconds (to complete the seed treatment). The treated seeds are then removed from the mixing chamber and dried in paper bags.

[0141] In all cases, the seed treatment dosage rate was 50 g safener / 100 kg seeds.

[0142] 2. Field trials

[0143] Seeds of eight TRZAW varieties treated with the safener described in heading 1 above, as well as untreated seeds, were planted in the field in strips, with four rows of TRZAW planted for each treatment. Four trials were conducted in various parts of Europe (Germany, France, Poland, and Italy).

[0144] The herbicide compound (2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-carboxylate (hereinafter “HER”), formulated as WP 20, was sprayed at a rate of 2 g ai / ha and an application volume of 200-300 l / ha in the early post-emergence stage (12 BBCH crops) and mid-post-emergence stage (13-31 BBCH crops). The herbicide was applied perpendicular to the planting strip containing the different seed treatments.

[0145] Visual assessment of crop damage from herbicide application observed in different zones (with and without seed treatment) compared to control zones (no herbicide application but with and without seed treatment).

[0146] The values ​​in the table below are the averages of two repeated experiments.

[0147] The effectiveness of the safety agent treatment is shown in Tables 3 and 4 below:

[0148] [Average Crop Damage]% = (Herbium damage on the herbicide-treated strip (with and without safener seed treatment)) Herbicide damage on untreated strips (with and without safener seed treatment) * 100

[0149] The herbicidal activity (%) of Alopecurus myosuroides (ALOMY) and oats (AVESA) was determined by the overall difference (%) between herbicide-treated and untreated plots in biomass and other symptoms (i.e., yellowing, necrosis, growth inhibition).

[0150] Table 3: Average maximum crop damage and weed control effect of TRZAW 12 BBCH (8 varieties of TRZAW)

[0151]

[0152] Table 4: Average maximum crop damage and weed control effect of TRZAW 21 BBCH (8 varieties of TRZAW)

[0153]

[0154] Unexpectedly, as shown in the table above, safer compound A3 provides greater safety for crops compared to safeners pyrazosulfuron or quinalazine.

[0155] Meanwhile, the herbicidal activity of HER is not affected by the safener compound A3.

[0156] B. Efficacy of different methods of applying safety agents

[0157] The following experiments were conducted using seeds of the winter wheat variety RGT Reform.

[0158] 1) Treat seeds with a safener in SC formulation, equivalent to 0.5 g of safener per kilogram of seeds.

[0159] 2) Treat the seeds with the appropriate amount of SC formulation without safener.

[0160] Place 5 treated seeds per pot on top of soil in a 3-liter plastic pot, cover with a soil-sand mixture, and grow in a climate chamber (daytime temperature: 16°C, nighttime temperature: 12°C, relative humidity: 50%, daylight hours: 15 hours).

[0161] When the plants reach the growth stage BBCH 10, they are transferred to a climate chamber with different climate settings (daytime high temperature: 15°C, nighttime temperature drops to 8°C, daytime relative humidity: 50-65%, nighttime relative humidity: 70%, daytime hours: 12 hours).

[0162] The experimental plants were treated after emergence during the growth stage of BBCH 11.

[0163] The herbicides and safeners used are prepared as follows:

[0164] “HER” ((2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid methyl ester): EC 10 g / l

[0165] "Compound A3" (see Table 2 above): WP20

[0166] These preparations are mixed according to the prescribed dosage and sprayed on the aboveground parts of the plants as an aqueous suspension at a water application rate of 200 l / ha, with the addition of a wetting agent (Mero, 1.5 l / ha).

[0167] The application rate of HER was 2 g / ha; the application rate of compound A3 was 50 g / ha.

[0168] Following application, the plants were continued to be cultivated as described above. Twenty-eight days after application, herbicide damage was visually assessed. Damage was evaluated visually on a scale of 0-100% compared to control plants that had not received herbicide and safener treatment.

[0169] 0% = No effect observed compared to untreated plants.

[0170] 20% = Compared with the untreated control group, the treated group suffered 20% damage (e.g., growth height, leaf damage, etc.).

[0171] 100% = The treated plants are completely damaged or dead.

[0172] Table 5 below lists the average values ​​from three replicates (3 pots, 5 plants per pot). The combination of seed treatment and subsequent foliar application showed significant superiority compared to the corresponding safener treatment alone.

[0173] Table 5: Crop Damage and Weed Control Effects of TRZAW Cultivars RGT Reform

[0174]

[0175] Compared to tank mixing of the safener with the herbicide, applying the safener as a seed treatment can unexpectedly reduce crop damage. By applying the safener twice (both as a seed treatment and as a tank-mixed herbicide), unexpected and even further reductions in crop damage were achieved.

Claims

1. A method for reducing crop damage, comprising treating crop seeds with a safener compound of formula (II) prior to sowing, in (R 1' ) n' -Phenyl groups are represented by one of the groups from Q-1.1 to Q-1.

55. Furthermore, (R) 2' ) m' -The phenyl group is selected from one of the groups Q-2.1 to Q-2.

55. R 3' It is hydrogen. and R 4' The following are the compounds: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, phenyl, benzyl, CH2(4-Cl-Ph), CH2(4-F-Ph), CH2(4-OMe-Ph), 2-methoxyethyl, tetrahydrofuran-2-yl-methyl, tetrahydrofuran-3-yl-methyl, tetrahydropyran-2-yl-methyl, tetrahydropyran-3-yl-methyl, tetrahydropyran-4-yl-methyl, methylpropionate-3-yl, ethylpropionate-3-yl, methylacetate-2-yl, ethylacetate-2-yl, methylneoplastate-2-yl, ethylneoplastate. -3-yl, methyl-2-methylpropionate-3-yl, methyl-2,2-dimethylpropionate-3-yl, ethyl-2-methylpropionate-3-yl, methyl-2-propionate-2-yl, ethyl-2-propionate-2-yl, methyl acetate-2-yl, ethyl acetate-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylate-2-yl, 2-(dimethylamino)ethyl, oxetane-3-yl, (3-methyloxetane-3-yl)methyl, 2,2,2-trifluoroethyl, 2,2-difluoro Ethyl, 2-fluoroethyl, 2,2,3,3,3-pentafluoropropyl, cyclopropylmethyl, 1-cyclopropylethyl, (1-methyl-cyclopropyl)-methyl, (2,2-dichlorocyclopropyl)-methyl, (2,2-dimethyl-cyclopropyl)methyl, allyl, propyne-propynyl (prop-2-yn-1-yl), 2-chloroprop-2-en-1-yl, 3-phenylprop-2-yn-1-yl, 3,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-fluoroprop-2-en-1-yl, methylprop-2-yn-1-yl, 2-methylprop-2-en-1-yl, but-2 -en-1-yl, but-3-en-1-yl, but-2-yn-1-yl, but-3-yn-1-yl, 4-chloro-but-2-yn-1-yl, 3-methyl-but-2-en-1-yl, 3-methyl-but-1-en-1-yl, 1-(2e)-1-methyl-but-2-en-1-yl, (e)-pent-3-en-2-yl or (z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, hept-2-yl, isobutyl, 1,3-dioxolanecyclo-2-ylmethyl or 1-ethyl-5-methyl-1H-pyrazole-4-methyl; Subsequently, a herbicide of formula (I) or its agrochemically acceptable salt is applied after sowing. in G represents OR 4 or NR 7 R 8 ; R 1 and R 2 Each represents hydrogen; R 3 The term represents (C1-C5)-alkyl, (C3-C6)-cycloalkyl, (C2-C5)-alkenyl, (C2-C5)-alkynyl, or (C1-C5)-alkoxy, each of which is optionally substituted "m" times with a substituent selected from halogen, cyano, (C1-C5)-alkoxy, and hydroxyl. R 4 It represents hydrogen. Or it can mean (C1-C) 12 (C3-C7)-alkyl, (C3-C7)-cycloalkyl-(C1-C8)-alkyl, (C2-C8)-alkenyl, (C5-C6)-cycloalkenyl, (C1-C4)-alkylphenyl, or (C2-C8)-ynyl, each optionally selected from halogen, cyano, (C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl, hydroxyl, S(O) n R 5 The substituents are replaced "m" times; R 5 The designation represents (C1-C8)-alkyl, (C2-C8)-alkenyl, (C3-C6)-cycloalkyl, benzyl, CON((C1-C3)-alkyl)2 or (C1-C8)-alkyl-C(O)-(C1-C8)-alkyl, each of which is optionally substituted "m" times by a substituent selected from halogens and cyano groups; R 6 It represents hydrogen. Or it may represent (C1-C8)-alkyl, (C3-C6)-cycloalkyl, (C3-C8)-alkenyl or (C3-C8)-ynyl, each of which is optionally substituted "m" times by a substituent selected from halogen, cyano and (C1-C2)-alkoxy. R 7 R 8 Each of these can be independently represented as hydrogen, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkyl, N((C1-C3)-alkyl)2, or S(O). n R 5 , or R 7 and R 8 Together with the nitrogen atoms they are attached to, they form saturated, partially unsaturated, or fully unsaturated five-, six-, or seven-membered rings. These rings, in addition to nitrogen atoms, may contain "r" carbon atoms and "o" oxygen atoms, and are optionally selected from halogens, (C1-C6)-alkyl groups, halo-(C1-C6)-alkyl groups, oxo groups, and CO2R groups. 6 The substituents are replaced "m" times; Z indicates that the selection is from Z-1 to Z-8: The arrows indicate the bonds that connect to the CO-G group in formula (I); X 2 X 4 and X 6 They can represent hydrogen or fluorine independently; X 3 and X 5 Each can be represented independently as hydrogen, chlorine, cyanide, or fluorine; or It represents (C1-C3)-alkyl, (C1-C3)-alkoxy, each of which is optionally substituted "m" times by a substituent selected from fluorine or chlorine; m represents 0, 1, 2, 3, 4 or 5; n represents 0, 1, or 2; o represents 0, 1, or 2; r represents 3, 4, 5, or 6.

2. The method according to claim 1, wherein the compound of formula (I) is a compound of formula (Ia) or an agriculturally chemically acceptable salt thereof. in X 3 X 5 R 3 And G as described above; Z represents Z-1a, Z-1b, Z-2a, Z-3a, Z-4a, Z-5a, Z-6a, Z-7a, Z-8a, Z-4a represents a mixture of the two structures Z-4b and Z-4c. Furthermore, Z-8a represents a mixture of the Z-8b and Z-8c structures. Furthermore, the arrows indicate bonds attached to the CO-G group in formula (Ia).

3. The method according to claim 1 or 2, wherein the compound of formula (I) is selected from: methyl rel-(2R,4R)-4-[[3-(3,5-dichlorophenyl)-5-methoxy-4H-isoxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylate, methyl rel-(2R,4R)-4-[[3-(3,5-dichlorophenyl)-5-vinyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylate, (2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid methyl ester, rel-(2R,4R)-4-[[3-(3-fluorophenyl)-5-methyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylic acid isopropyl ester, (3R)-3-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazol-5-carbonyl]amino]-2,3-dihydrofuran-5-carboxylic acid methyl ester, and (3R)-3-[[(5R)-3-(3,5-difluorophenyl)-5-methyl-4H-isoxazole-5-carbonyl]amino]-2,3-dihydrofuran-5-carboxylic acid methyl ester.

4. The method according to any one of the preceding claims, wherein the compound of formula (II) is selected from: Methyl-{[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, {[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid, Methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid, Methyl-{[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, {[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid, Methyl-{[5-(4-bromo-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, {[5-(4-bromo-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid, Methoxyethyl-{[1-(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, and {[1-(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid.

5. The method according to any one of the preceding claims, wherein the herbicidal compound of formula (I) is methyl (2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isoxazole-5-carbonyl]amino]tetrahydrofuran-2-carboxylate, and / or wherein the safener compound of formula (II) is selected from... Methyl-{[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, Methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, Methyl-{[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, methyl-{[5-(4-bromo-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate, and Methoxyethyl-{[1-(4-bromo-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate.

6. The method according to claim 5, wherein the herbicidal compound of formula (I) is (2R*,4R*)-4-[[(5S)-3-(3,5-difluorophenyl)-5-vinyl-4H-isooxazol-5-carbonyl]amino]tetrahydrofuran-2-carboxylate, and wherein the safener compound of formula (II) is methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate.

7. The method according to any one of claims 1 to 6, wherein the herbicidal compound of formula (I) is applied in a pre-emergence treatment.

8. The method according to any one of claims 1 to 6, wherein the herbicidal compound of formula (I) is applied in a post-emergence treatment.

9. The method according to any one of the preceding claims, wherein the crop is a genetically modified plant.

10. The method according to any one of the preceding claims, wherein the safener compound of formula (II) is applied to the seeds at an application rate of 0.01 to 2 g / kg of seeds, preferably 0.1 to 1 g / kg of seeds.

11. The method according to any one of the preceding claims, wherein the herbicidal compound of formula (I) is applied at an application rate of 0.1 to 1000 g / ha, preferably 1 to 50 g / ha.

12. The method according to any one of the preceding claims further includes applying the safety agent compound of formula (II) in a pre-emergence treatment or post-emergence treatment after sowing.

13. The method of claim 12, wherein the safener compound of formula (II) is applied together with the herbicidal compound of formula (I) in the form of a tank mix.

14. The method according to any one of the preceding claims, wherein the crop is selected from wheat, black wheat, barley and rye.

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