Mixtures comprising an azine compound for selective weed control in rice

Abstract

A method for selectively controlling weeds in rice, which method comprises applying to the crop cultivation area an effective amount of a herbicidal mixture comprising as component 1) a herbicide A of the formula (I) and as component 2) at least one further compound selected from the group of compounds B, wherein R 1 to R 8 are as defined above.(I)

Description

[0001] The present invention relates to a method for selectively controlling weeds in rice, the method comprising applying an effective amount of a herbicidal mixture to a rice cultivation area where weeds grow or may grow as described herein, the herbicidal mixture comprising herbicide A as component 1) and at least one other compound selected from compound B as component 2).

[0002] The present invention also relates to the use of the herbicidal mixture for selective weed control in rice. Background Technology

[0003] In crop protection products, it is desirable, in principle, to improve the specificity and reliability of the active compound's action. Specifically, it is desirable for the crop protection product to effectively control harmful plants while simultaneously being tolerated by the beneficial plants in question. It is known that in some cases, better crop-plant compatibility can be achieved by combining a specifically acting herbicide with an organic active compound acting as an antidote or antagonist. Because these antidotes or antagonists can reduce or even prevent damage to crop plants, they are also referred to as safeners.

[0004] Generally, herbicides or herbicides are preferred for their effectiveness in controlling unwanted vegetation while simultaneously exhibiting acceptable phytotoxicity to crop plants.

[0005] WO 2022 / 161801 discloses certain acridine compounds for controlling unwanted vegetation and compositions comprising these acridine compounds. While these acridine compounds exhibit excellent herbicidal activity, there remains a need for methods to selectively control weeds in rice that provide effective control of unwanted vegetation while being well tolerated by rice. Summary of the Invention

[0006] The object of the present invention is to provide a method for selectively controlling weeds in rice using a herbicidal mixture containing azazine compounds, which allows for effective and reliable control of weeds that are growing or may grow in the rice planting area and are well tolerated by the rice.

[0007] Furthermore, the method should allow for effective weed control in the rice paddies without the need for a safener to prevent or reduce damage to the rice. However, in some cases, a safener may be used if necessary.

[0008] In addition, the herbicidal activity of the composition should last long enough to achieve weed control over a sufficiently long period of time, thereby allowing for more flexible application.

[0009] Surprisingly, it has now been found that selective control of weeds growing or about to grow in rice cultivation areas can be achieved by applying an effective amount of a herbicide mixture to the crop cultivation area, the herbicide mixture comprising herbicide A as component 1), which is selected from compounds having formula (I) and salts of compounds having formula (I).

[0010]

[0011] (I)

[0012] in

[0013] R 1 It is F;

[0014] R 2 Choose the group composed of free hydrogen and halogens;

[0015] R 3 It is H, F;

[0016] R 4 Choose the group composed of F, Cl, Br, and I;

[0017] R 5 Choose from the group consisting of hydrogen, halogens, and C1-C6-alkyl groups;

[0018] R 6 The group consisting of H, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy is selected.

[0019] R 7 The group consisting of H, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy is selected.

[0020] R 8 Selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, and C2-C6-ynyl groups.

[0021] In a preferred embodiment of the method according to the invention, the effective amount of herbicide A is selected from compounds having formula (I) and salts of compounds having formula (I), wherein

[0022] R 1 It is F;

[0023] R 2 It is halogen;

[0024] R 3 It is H, F;

[0025] R 4Choose the group composed of F, Cl, Br, and I;

[0026] R 5 It is halogen;

[0027] R 6 It is a C1-C6-alkyl group;

[0028] R 7 It is a C1-C6-alkyl group;

[0029] R 8 It is a C1-C6-alkyl group; and

[0030] As component 2), at least one other compound selected from compound B:

[0031] B1) Selected from the group of lipid biosynthesis inhibitors: cyhalofop-butyl, cyclobenzanone, fenvalerate, and clodinafop-propargyl;

[0032] B2) Group selected from ALS inhibitors: bispyribac-sodium, bensulfuron-methyl, ethoxysulfuron, methyl imazalil, imazalilnic acid, imazalil, promethazine, pyrimisulfuron, fluazinam;

[0033] B3) Selected from the photosynthesis inhibitor group: atrazine, cyclomethazine, metribuzin, diuron, betazon, and betazon-sodium;

[0034] B4) Selected from the group of protoporphyrinogen-IX oxidase inhibitors: flupyrimichlor, propyzoxyl, bispyribac-methyl, pyrimisulfuron-methyl, trifluralin, 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridyl]oxy]phenoxy]ethyl acetate (CAS 2158274-50-9);

[0035] B5) Selected from the group of bleaching agents and herbicides:

[0036] PDS inhibitors: flubutyrazole, dichlorvos, pyrfluthrin, flupyrfluthrin, flurfluthrin, furazolidone, dapoxetine, flupyrfluthrin, 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33-7), limexafine; HPPD inhibitors: bicyclosulfuron, isoxaflutole, mesosulfuron, cyclosulfuron, pyridinesulfuron, benzoxazine.

[0037] B6) Group from EPSP synthase inhibitors:

[0038] Glyphosate, glyphosate-isopropylammonium, glyphosate-potassium and glyphosate-trimethyl sulfide (thiophos);

[0039] B7) Group from glutamine synthase inhibitors:

[0040] Glufosinate, granulated glufosinate, glufosinate-ammonium and granulated glufosinate-ammonium.

[0041] B9) Selected from the group containing mitosis inhibitors:

[0042] Compounds in group K1: pendimethalin, trifluralin, and icafolin methyl.

[0043] B10) Selected from the VLCFA inhibitor group:

[0044] Butachlor, S-methylphenidate, S-metolachlor, propachlor, sulfonylpyrazosulfuron;

[0045] B13) Selected from the group of plant growth regulator herbicides:

[0046] 2,4-D and its salts and esters, such as clacyfos, 2,4-DB and its salts and esters, dicamba and its salts and esters, and chlorpyrifos.

[0047] B15) Selected from other herbicides: bromobutide, chlorflurenol, cyclohexane, tetraflufenican.

[0048] In a more preferred embodiment of the method according to the invention, an effective amount of herbicide A is used, which herbicide A is selected from compounds having formula (I) and salts of compounds having formula (I), wherein

[0049] R 1 It is F;

[0050] R 2 It is F;

[0051] R 3 It is H, F;

[0052] R 4 Choose the group composed of F, Cl, and Br;

[0053] R 5 It is F;

[0054] R 6 It is a C1-C6-alkyl group;

[0055] R 7 It is a C1-C6-alkyl group.

[0056] In a particularly preferred embodiment of the method according to the invention, herbicide A is a compound having formula (Ia) or a salt of a compound having formula (Ia).

[0057] .

[0058] In another particularly preferred embodiment of the method according to the invention, herbicide A is a compound having formula (Ib) or a salt of a compound having formula (Ib).

[0059] .

[0060] In another particularly preferred embodiment of the method according to the invention, herbicide A is a compound having formula (Ic) or a salt of a compound having formula (Ic).

[0061] .

[0062] In another particularly preferred embodiment of the method according to the invention, herbicide A is a compound having formula (Id) or a salt of a compound having formula (Id).

[0063] .

[0064] In the method according to the invention, the required amount of the pure active compound (i.e., herbicide A) depends on the density of the unwanted vegetation, the developmental stage of the plant, the climatic conditions of the location where the composition is used, and the method of application.

[0065] In another particularly preferred embodiment of the method according to the invention, herbicide B is selected from the following compound B:

[0066] Cyfluthrin, Cyclobutrazol;

[0067] Benzylsulfuron, bispyribac-sodium, ethoxysulfuron, promethazine-sulfuron, pyrimisulfuron;

[0068] Thiamethoxam and thiamethoxam-sodium;

[0069] Bismuth subtilis and pyrimethanil;

[0070] Bicyclosulfuron;

[0071] Metformin;

[0072] Butachlor and pretilachlor;

[0073] chloropyridine benzyl ester;

[0074] Cyclohexane and tetraflufenican.

[0075] The herbicide mixture of the present invention can generally be applied to weeds at any growth stage with good results. In one embodiment, application of the herbicide mixture up to weed growth stage 37 shows effective weed control.

[0076] This invention relates to a method for selectively controlling weeds in rice.

[0077] In the method for selectively controlling weeds in rice according to the invention, the herbicidal mixture can generally be applied before and / or after crop emergence, up to crop growth stage 29-37.

[0078] Weeds controlled by the method according to the invention include monocotyledonous and dicotyledonous plants.

[0079] Compared with methods of applying herbicides with similar structures, the method of the present invention for selectively controlling weeds in rice has several advantages:

[0080] - The method of the present invention shows excellent crop compatibility with certain conventional crop plants, especially rice.

[0081] Therefore, the method of the present invention can also be applied not only before emergence but also after crop emergence, without the addition of a safener to provide greater timing flexibility.

[0082] - The method of the present invention provides sufficient duration of weed-controlling activity, even under severe weathering conditions, allowing for more flexible application and minimizing the risk of weed escape. Detailed Implementation

[0083] This invention relates to a method for selectively controlling weeds in rice, the method comprising applying an effective amount of a herbicide mixture to a crop cultivation area, the herbicide comprising herbicide A selected from compounds having formula (I) and salts of compounds having formula (I).

[0084]

[0085] (I)

[0086] in

[0087] R 1 It is F;

[0088] R 2 Choose the group composed of free hydrogen and halogens;

[0089] R 3 It is H, F;

[0090] R 4 Choose the group composed of F, Cl, Br, and I;

[0091] R 5 Choose from the group consisting of hydrogen, halogens, and C1-C6-alkyl groups;

[0092] R 6 The group consisting of H, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy is selected.

[0093] R 7 The group consisting of H, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy is selected.

[0094] R 8 Selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, and C2-C6-ynyl groups, and

[0095] As component 2), at least one other compound selected from compound B:

[0096] B1) Selected from the group of lipid biosynthesis inhibitors: cyhalofop-butyl, cyclobenzanone, fenvalerate, and clodinafop-propargyl;

[0097] B2) Group selected from ALS inhibitors: bispyribac-sodium, bensulfuron-methyl, ethoxysulfuron, methyl imazalil, imazalilnic acid, imazalil, promethazine, pyrimisulfuron, fluazinam;

[0098] B3) Selected from the photosynthesis inhibitor group: atrazine, cyclomethanone, cypermethrin, diuron, thiamethoxam and thiamethoxam-sodium;

[0099] B4) Selected from the group of protoporphyrinogen-IX oxidase inhibitors: flupyrimichlor, propyzoxyl, bispyribac-methyl, pyrimisulfuron-methyl, trifluralin, 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridyl]oxy]phenoxy]ethyl acetate (CAS 2158274-50-9);

[0100] B5) Selected from the group of bleaching agents and herbicides:

[0101] PDS inhibitors: flubutyrazole, dichlorvos, pyrfluthrin, flupyrfluthrin, flurfluthrin, furazolidone, dapoxetine, flupyrfluthrin, 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33-7), limexafine; HPPD inhibitors: bicyclosulfuron, isoxaflutole, mesosulfuron, cyclosulfuron, pyridinesulfuron, benzoxazine.

[0102] B6) Group from EPSP synthase inhibitors:

[0103] Glyphosate, glyphosate-isopropylammonium, glyphosate-potassium and glyphosate-trimethyl sulfide (thiophos);

[0104] B7) Group from glutamine synthase inhibitors:

[0105] Glufosinate, granulated glufosinate, glufosinate-ammonium and granulated glufosinate-ammonium.

[0106] B9) Selected from the group containing mitosis inhibitors:

[0107] Compounds in group K1: pendimethalin, trifluralin, and isoxaflutole methyl ester;

[0108] B10) Selected from the VLCFA inhibitor group:

[0109] Butachlor, S-methylphenidate, S-metolachlor, propachlor, sulfonylpyrazosulfuron;

[0110] B13) Selected from the group of plant growth regulator herbicides:

[0111] 2,4-D and its salts and esters, such as chlorpyrifos, 2,4-DB and its salts and esters, dicamba and its salts and esters, and chlorpyrifos.

[0112] B15) Selected from other herbicides: bromobutyroxyfen, chlorpyrifos, cyclohexane, tetraflufenoxam.

[0113] Furthermore, this invention relates to agrochemical compositions for selective weed control in rice, these agrochemical compositions comprising the herbicidal mixture of the present invention and one or more adjuvants commonly used in crop protection compositions. Furthermore, this invention relates to the use of said compositions for selective control of weeds in rice.

[0114] As used in this article, the terms “control” and “counter” are synonyms, referring to the inhibition, control, reduction or complete destruction of weed growth.

[0115] As used herein, the terms "composition of herbicide A" and "composition containing herbicide A" refer to any composition containing herbicide A. Different salts of herbicide A are considered to be the same herbicide compound.

[0116] As used herein, the term "agricultural chemical composition" refers to a composition of herbicide A (and compositions comprising herbicide A) and one or more adjuvants commonly used in crop protection compositions.

[0117] As used herein, "herbicide" means one or more reagents, compounds and / or compositions that have herbicidal and / or herbicidal activity.

[0118] As used herein, the terms “undesirable vegetation,” “undesirable species,” “undesirable plant,” “harmful plant,” “undesirable weed,” “native plant,” “weed,” or “harmful weed” are used synonymously.

[0119] As used in this article, "post-emergence" refers to herbicide treatment applied to areas where weeds have already germinated and emerged from the ground or growing medium.

[0120] As used in this article, "pre-emergence" refers to herbicide treatment applied to areas where weeds have already germinated and are emerging from the ground or growing medium.

[0121] As used in this article, "de-germination" refers to the use of herbicides to reduce the presence of weeds during treatment. De-germination is typically used in minimally tilled or no-till fields because weeds cannot be controlled by tilling the soil. De-germination can be applied after harvest and / or before crop emergence. De-germination is particularly useful for weeds that appear between growing seasons.

[0122] Throughout this specification and in connection with the compound or molecular portion, the prefix "C" is used. n -C m "Each indicates the range of possible carbon atoms that a molecular moiety or compound can have. The term 'C1-C'..." n "-alkyl" indicates a group of straight-chain or branched saturated hydrocarbon groups having 1 to n carbon atoms.

[0123] Examples of this meaning are:

[0124] -C1-C3-alkyl and the C1-C3-alkyl moiety of di(C1-C3-alkyl)amino, C1-C3-alkoxy-C1-C3-alkyl: for example CH3, C2H5, n-propyl and CH(CH3)2;

[0125] -C1-C4-alkyl: for example CH3, C2H5, n-propyl, CH(CH3)2, n-butyl, CH(CH3)-C2H5, CH2-CH(CH3)2 and C(CH3)3;

[0126] -C1-C6-alkyl and also C1-C6-cyanoalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy-C1-C6-alkyl, di(C1-C6-alkoxy)C1-C6-alkyl, C1-C6-haloalkoxy-C1-C6-alkyl, C3-C6-enoxy-C1-C6-alkyl, C3-C6-haloenoxy-C1-C6-alkyl, C3-C6- Alkenoxy-C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylthio-C1-C6-alkyl, C1-C6-alkylsulfinyl-C1-C6-alkyl, C1-C6-alkylsulfonyl-C1-C6-alkyl, C1-C6-alkylcarbonyl-C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl, C1-C6-haloalkoxycarbonyl-C1-C6-alkyl, C3-C6-alkenoxycarbonyl -C1-C6-alkyl, C3-C6-alkynoxycarbonyl-C1-C6-alkyl C1-C6-alkyl C1-C6-alkyl moiety: as mentioned above, C1-C4-alkyl, and also such as n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 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 or 1-ethyl-2-methylpropyl, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1,1-dimethylethyl, n-pentyl or n-hexyl;

[0127] -C1-C3-Haloalkyl: C1-C3-alkyl groups as mentioned above that are partially or wholly substituted with fluorine, chlorine, bromine and / or iodine, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl 2,2-Dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl;

[0128] -C1-C4-Haloalkyl: C1-C4-alkyl groups as mentioned above, partially or wholly substituted with fluorine, chlorine, bromine and / or iodine, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2- Fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 1,1,2,2-tetrafluoroethyl and 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl;

[0129] -C1-C6-haloalkyl: C1-C4-haloalkyl as mentioned above, and also, for example, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecylfluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;

[0130] -C1-C3-alkoxy and the C1-C3-alkoxy moiety of C1-C3-alkoxy-C1-C3-alkyl, C1-C3-alkoxycarbonyl: for example, methoxy, ethoxy, propoxy;

[0131] -C1-C4-alkoxy compounds: such as methoxy, ethoxy, propoxy, 1-methylethoxybutoxy, 1-methylpropoxy, 2-methylpropoxy, and 1,1-dimethylethoxy;

[0132] -C1-C6-alkoxy and also C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy-C1-C6-alkyl, di(C1-C6-alkoxy)C1-C6-alkyl, C3-C6-enoxy-C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl C1-C6-alkyl moiety: as mentioned above, C1-C4-alkoxy, and also, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxybutoxy, 1,1-dimethyl... 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 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.

[0133] -C1-C3-Haloalkoxy: C1-C3-alkoxy groups mentioned above that are partially or wholly substituted with fluorine, chlorine, bromine, and / or iodine, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2, 2-Trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy;

[0134] -C1-C4-Haloalkoxy: C1-C4-alkoxy groups as mentioned above that are partially or wholly substituted with fluorine, chlorine, bromine, and / or iodine, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy 2-Fluoropropoxy, 3-Fluoropropoxy, 2-Chloropropoxy, 3-Chloropropoxy, 2-Bromopropoxy, 3-Bromopropoxy, 2,2-Difluoropropoxy, 2,3-Difluoropropoxy, 2,3-Dichloropropoxy, 3,3,3-Trifluoropropoxy, 3,3,3-Trichloropropoxy, 2,2,3,3,3-Pentafluoropropoxy, Heptafluoropropoxy, 1-(Fluoromethyl)-2-Fluoroethoxy, 1-(Chloromethyl)-2-Chloroethoxy, 1-(Bromomethyl)-2-Bromoethoxy, 4-Fluorobutoxy, 4-Chlorobutoxy, 4-Bromobutoxy and Nonafluorobutoxy;

[0135] -C1-C6-haloalkoxy and the C1-C6-haloalkoxy-C1-C6-alkyl, C1-C6-haloalkoxycarbonyl-C1-C6-alkyl C1-C6-haloalkoxy moiety: as mentioned above, C1-C4-haloalkoxy, and also, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecylfluoropentoxy, 6-fluorohexyloxy, 6-chlorohexyloxy, 6-bromohexyloxy, 6-iodohexyloxy and dodecafluorohexyloxy.

[0136] In the context of this invention, azazine compounds having formula (I) (herbicide A) may be used as is or in the form of their agriculturally acceptable salts. Suitable are typically salts of those cations whose cations and anions do not adversely affect the activity of the active compound, and acid addition salts of those acids.

[0137] Preferred cations are alkali metal ions, preferably lithium, sodium, and potassium ions; alkaline earth metal ions, preferably calcium and magnesium ions; and transition metal ions, preferably manganese, copper, zinc, and iron ions. Additionally, ammonium and substituted ammonium compounds in which one to four hydrogen atoms are replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl, or benzyl groups are preferred. Specifically, ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tri(isopropyl)ammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, and tetraethylammonium are preferred. Salts of methylammonium, tetrabutylammonium, 2-hydroxyethylammonium (ethanolamine salt), 2-(2-hydroxyethyl-1-oxy)ethyl-1-ylammonium (diethylene glycolamine salt), di(2-hydroxyethyl-1-yl)ammonium (diethanolamine salt), tri(2-hydroxyethyl)ammonium (triethanolamine salt), tri(2-hydroxypropyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N,N-trimethylethanolammonium (choline salt), as well as phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, such as trimethylsulfonium, and sulfonium oxide ions, preferably tri(C1-C4-alkyl)sulfonium oxide, and finally polyamines such as salts of N,N-bis-(3-aminopropyl)methylamine and diethylenetriamine.

[0138] The useful anions of acid addition salts are mainly chloride, bromide, fluoride, iodide, hydrogen sulfate, methyl sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.

[0139] In the method according to the invention, the required amount of the pure active compound (i.e., herbicide A) depends on the density of the unwanted vegetation, the developmental stage of the plant, soil characteristics, climatic conditions of the site where the composition is used, and the method of application.

[0140] Typically, the application rate of herbicide A is from 1 to 500 g / ha, preferably from 1 to 250 g / ha, and more preferably from 1 to 100 g / ha of active substance.

[0141] In a specific embodiment of the method according to the invention, herbicide A is applied after rice emergence at a rate of 2 g / ha to 40 g / ha, preferably at a rate of 4 to 20 g / ha.

[0142] The application rate of the herbicides mentioned above indicates the amount of active agent without adjuvants (such as carrier materials or surfactants).

[0143] The herbicide mixture comprises, as component 1), herbicide A selected from compounds having formula (I) and salts of compounds having formula (I), and as component 2), at least one additional compound selected from compound B, wherein the relative ratio of components 1) : 2) by weight is generally in the range of 1:1000 to 1000 : 1, preferably in the range of 1:500 to 500 : 1, particularly in the range of 1:250 to 250 : 1, and especially preferably in the range of 1:75 to 75 : 1.

[0144] In one embodiment of the method according to the invention, the ratio of herbicide A to herbicide B in the mixture is from 10:1 to 1:1500.

[0145] In another embodiment of the method according to the invention, the ratio of herbicide A to herbicide B in the mixture is from 3:1 to 1:500.

[0146] Particularly preferred mixtures for use in this invention are listed in Table A below:

[0147] Table A

[0148]

[0149] Particularly preferred mixtures for use in this invention are listed in Table B below:

[0150] Table B

[0151]

[0152] In another embodiment of the invention, the composition according to the invention optionally contains at least one safety agent S.

[0153] According to another preferred embodiment of the invention, in addition to components 1), 2), and 3), the composition optionally contains at least one, and in particular exactly one, safer S, which is specifically selected from the group consisting of: oxazin, oxalic acid, cyclopropanesulfonamide, dichloropropyleneamine, oxazolium, oxazinidine, oxazolazole, bis(oxazolyl)acrylic acid, pyrazole oxazolyl, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4).

[0154] Safeguards are chemical compounds that prevent or reduce damage to beneficial plants without significantly affecting the herbicidal activity of the herbicidal active component of the composition of the invention against unwanted plants. They can be applied before sowing (e.g., on seed treatment, cuttings, or seedlings), or before or after emergence of the beneficial plants.

[0155] Suitable safers are, for example, (quinoline-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide, α-oxime-phenylacetonitrile, acetophenone oxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzamide, 1,8-naphthalenedicarboxylic anhydride, 2-halo-4-(haloalkyl)-5-thiazolic acid, thiophosphates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and agriculturally acceptable derivatives, such as amides, esters and thioesters, provided that they have an acid group.

[0156] Examples of preferred safener S are fenchlorfon, fenchloric acid, fenchlorfenazate, cyclopropanesulfonamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalenecarboxylic anhydride, fenchlorfenazate, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), and 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 71526-07-3). 52836-31-4), sulfanilamide and BPCMS (CAS54091-06-4).

[0157] The particularly preferred safer agents S are oxazin, oxazolidinyl sulfonamide, cyclopropanesulfonamide, dichloropropeneamine, oxazolyl sulfonamide, oxazolidinyl sulfonamide, oxazolidinyl sulfonamide, fluroxypyr, oxazolidinyl sulfonamide, bis(oxazolidinyl sulfonamide), pyrazole oxazolidinyl sulfonamide, naphthalenecarboxylic anhydride, oxazolidinyl sulfonamide, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4), and oxazolidinyl sulfonamide.

[0158] The particularly preferred safer agent S is oxalic acid, cyclopropanesulfonamide, oxalidone, oxaloxazole, bis(oxazolyl) ethyl ester, and pyrazole oxalic acid diethyl ester.

[0159] Particularly preferred safety agent S, as component S, is an ingredient in the composition according to the invention, and is safety agent S as defined above; particularly, safety agents S.1-S.17 are listed in the following table:

[0160] Table S

[0161]

[0162] In a ternary composition comprising at least one component 1), component 2), and a safer S, the weight ratio of component 1):2) is generally in the range of 1:1000 to 1000:1, preferably in the range of 1:500 to 500:1, particularly in the range of 1:250 to 250:1, and especially preferably in the range of 1:75 to 75:1; the weight ratio of component 1):S) is generally in the range of 1:1000 to 1000:1, preferably in the range of 1:500 to 500:1, particularly in the range of 1:250 to 250:1, and especially preferably in the range of 1:75 to 75:1; and the weight ratio of component 2):S) is generally in the range of 1:1000 to 1000:1, preferably in the range of 1:1000 to 1000:1, and especially preferably in the range of 1:1000 to 1000:1. The weight ratio of component 1) + 2) to safety agent S) is preferably in the range of 500 to 500:1, particularly in the range of 1:250 to 250:1, and especially preferably in the range of 1:75 to 75:1.

[0163] The method or use of the present invention is particularly suitable for selectively controlling weeds, wherein herbicide A is applied to field areas where weeds are growing or may grow and rice cultures will be planted or have already been planted.

[0164] In a preferred embodiment of the method or use of the present invention, the herbicidal mixture is applied to an area where rice is grown.

[0165] Unless otherwise stated, the herbicidal mixture is suitable for application in any rice variety as outlined in this article, regardless of genetic background, hybridization, or breeding techniques.

[0166] In a preferred embodiment of the method according to the invention, an effective amount of the herbicidal mixture is applied to the crop cultivation area where rice is grown.

[0167] In another preferred embodiment of the method according to the invention, an effective amount of the herbicidal mixture containing compound (Ia) is applied to the crop cultivation area where rice is grown.

[0168] In another preferred embodiment of the method according to the invention, an effective amount of the herbicidal mixture containing compound (Ib) is applied to the crop cultivation area where rice is grown.

[0169] In another preferred embodiment of the method according to the invention, an effective amount of the herbicidal mixture containing compound (Ic) is applied to the crop cultivation area where rice is grown.

[0170] In another preferred embodiment of the method according to the invention, an effective amount of the herbicidal mixture containing compound (Id) is applied to the crop cultivation area where rice is grown.

[0171] The method according to the invention can be used to control a wide variety of harmful plants (undesirable vegetation), including monocotyledonous and dicotyledonous weeds, particularly for controlling weeds selected from the following genera: *Abutilon*, *Aisma*, *Alopecurus*, *Amaranthus*, *Ambrosia*, *Ammania*, *Ammi*, *Aneilema*, *Anthemis*, *Apera*, *Atriplex*, *Avena*, *Barbarea*, and *Bidow's Needle*. ens), Brassica, Bromus, Bunias, Butomus, Capsella, Centaurea, Chenopodium, Cirsium, Conium, Convolvolus, Cyperus, Datura, Daucus, Descurainia, Digitaria, Echinochloa, Eleocharis, and others The genera *Eleusine*, *Euphorbia*, *Fimbristylis*, *Fumaria*, *Galinsoga*, *Galium*, *Geranium*, *Heliotropium*, *Heteranthera*, *Hibiscus*, *Ipomea*, *Kochia*, *Lamium*, *Leptochloa*, *Leersia*, *Limnocharis*, and *Lolium* are all related to the plant family. The genera *Ludwigia*, *Lycopsis*, *Matricaria*, *Mercurialis*, *Monochoria*, *Orobanche*, *Panicum*, *Papaver*, *Poa*, *Polygonum*, *Portulaca*, *Raphanus*, *Sagittaria*, *Scirpus*, *Setaria*, *Sinapis*, and *Sphenoclea* are mentioned.The genera *Sonchus*, *Sisymbrium*, *Stachys*, *Stellaria*, *Thlaspi*, *Veronica*, *Viola*, and *Xanthium*.

[0172] According to one embodiment of the present invention, weeds including but not limited to the following species are selectively controlled: Abutilon theophrasti, Agropyron repens, Alopecurus myosuroides, Amaranthus hybridus, Amaranthus palmeri, Amaranthus retroflexus, Ambrosia artemisiifolia, Ambrosia trifida, Anagallis arvensis, Anchusa officinalis, Artemisia vulgaris, Atriplex patula, Bidens pilosa, Brachiaria decumbens, Brachiaria platyphylla, Calystegiasepium, and Capsella. Bursa-pastoris, Centrus echinatus, Chenopodium album, Chenopodium ficifolium, Chenopodium hybridum, Cirsium arvense, Convolvulus arvensis, Conyza bonariensis, Conyza canadensis, Cynodon dactylon, Cyperus esculentus, Datura stramonium, Digitaria sanguinalis, Echinochloa colonum, Echinochloa crus-galli, Equisetum arvensis, Euphorbia heterophylla, Galinsoga ciliata, Galinsoga parviflora, Galium aparine, Geranium dissectum, Ipomoea hederacea, Ipomoea rubrapurpurea, false burdock (Ivaxanthiifolia), Kochia scoparia, Lamium amplexicaule, Lamium purpureum, Matricaria inodora, Panicum dichotomiflorum, Pennisetum glaucum, Phalaris paradoxa, Poa annua, Polygonum aviculare, Polygonum convolvulus, Polygonum lapathifolium, Polygonum persicaria, Raphanus raphanistrum, Setaria faberi, Setaria glauca, Setaria verticillata, Setaria viridis, Sinapis Arvensis, Solanum nigrum, Sonchus arvensis, Sorghum bicolor, Sorghum halepense, Stachys annua, Stellaria media, Symphonytum officinale, Thraspi arvense, Veronicahederifolia, Veronica persica, Viola arvensis, Xanthium strumarium.

[0173] According to embodiments of the present invention, weeds including but not limited to the following monocotyledonous species are selectively controlled: *Cenchrus pauciflorus*, *Chloris virgata*, *Commelinaerecta*, *Bermudagrass*, *Cyperus spp.*, *Echinocloa colonum*, *Trichloris crinita*, *Digitaria insularis*, *Urochloa* or *Brachiaria decumbens*, *Cenchrus echinatus*, *Commelina benghalensis*, *Avena strigosa*, *Pennisetum americanum*, *Panicum maximum*, barnyard grass, *Urochloa platyphylla* or *Urochloa platyphylla*, *Digitaria spp.*, *Panicum*. spp.), large foxtail grass, goosegrass, false sorghum, multiflora ryegrass, ryegrass (Lolium spp.), lemma or brachiaria (Brachiaria spp.), bermudagrass, dragon claw grass (Dactyloctenium aegyptium), crabgrass, foxtail grass, dayflower (Commelina communis), tubular grass (Rottboellia cochinchinensis), foxtail (Setaria spp.), creeping icegrass (Agropyron repens or Elymus repens), flat crabgrass (Digitaria horizontalis), plantain (Urochloa plantaginea or plantain arm-shaped grass (Brachiaria plantaginea), fine-leaved leek (Leptochloa filiformis), leek (Leptochloa), barnyard grass (Echinochloa) spp.), spp., spp. or spp., barnyardgrass, barnyardgrass, and spiky foxtail.

[0174] According to a preferred embodiment of the present invention, weeds including, but not limited to, the following species are selectively controlled:

[0175] - Dicotyledonous species: *Aeschynomene denticulata*, *Abutilontheophrasti*, *Alternanthera sessilis*, *Amaranthus palmeri*, *Amaranthus retroflexus*, *Amaranthus tuberculatus*, *Amaranthus viridis*, *Ambrosia artemisiifolia*, *Ammannia auriculata*, *Ammannia baccifera*, *Ammannia multiflora*, *Eclipta prostrata*, *Euphorbia heterophylla*, *Lindernia procumbens*, *Ludwigia decurrens*, *Ludwigia hyssopifolia*, *Ludwigia pubescens* octovalvis), Ludwigia prostrata, Spermacoce verticillate, Sphenocleazeylanica, Trianthema portulacastrum;

[0176] - Monocotyledonous species (especially the following sedges): Cyperus difformis, Cyperus iria, Cyperus esculentus, Cyperus rotundus, Eleocharis acicularis, Eleocharis kuroguwai, Fimbristylismiliacea, Schoenoplectiella juncoides, Bolboschoenus planiculmis, Bolboschoenus maritimus, Schoenoplectiella mucronate;

[0177] - Monocotyledonous species (especially the following grasses): Cynodon dactylon, Dactyloctenium aegyptium, Echinochloa crus-galli, Echinochloacolonum, Eleusine indica, Ischaemum rugosum, Leptochloa fusca subsp. Fascicularis, Leptochloa fusca subsp. Uninervia, Leptochloa chinensis, Leersia hexandra, Paspalum distichum;

[0178] - Monocotyledonous species (excluding grasses or sedges): Alisma canaliculatum, Limnocharis flava, Pontederia korsakowii, Pontederia vaginalis, and Potamogeton distinctus.

[0179] Compositions containing herbicide (A) can generally be applied to weeds at any growth stage with good results. In one embodiment, application of the composition containing herbicide (A) up to weed growth stage 37 shows effective weed control. In a preferred embodiment, application of the composition containing herbicide (A) up to weed growth stage 32 shows effective weed control.

[0180] In the method for selective control of weeds in rice according to the invention, the composition containing herbicide (A) can generally be applied before and after crop emergence, up to the crop growth stage 37.

[0181] In a preferred embodiment, the composition comprising herbicide (A) is applied before crop emergence and after emergence at growth stages 00 to 32, particularly preferably at growth stages 12-14 to 21-29.

[0182] The composition of herbicide A can be applied in a conventional manner using techniques familiar to the technician. Suitable techniques include spraying, dripping, atomizing, dusting, broadcasting, or watering. The type of application depends on the intended purpose, and in any case, it should ensure the finest possible distribution of the active ingredient.

[0183] Compositions of herbicide A are applied to areas primarily by spraying, particularly by foliar spraying, using an aqueous dilution of the active ingredient. Application can be carried out using conventional spraying techniques, for example, water as a carrier and a spray rate of approximately 10 to 2000 l / ha or 50 to 1000 l / ha, for example, 100 to 500 l / ha. Application of compositions of herbicide A via low-volume and ultra-low-volume methods is possible, as is their application in particulate form.

[0184] If certain crop plants are poorly tolerant of the active ingredient, an application technique can be used where the herbicide A composition is sprayed using a spraying device to minimize contact (if any) with the leaves of sensitive crop plants, while simultaneously reaching the leaves of unwanted plants growing underneath or the bare soil (post-directed application, final field application). Another technique involves dripping herbicide A into the paddy field between crop rows using still water, allowing herbicide A to distribute throughout the field area, thus achieving effective weed control without harming the crop plants.

[0185] Another technique to provide additional selectivity under pre-emergence / pre-planting conditions can be achieved by first applying the active ingredient and then removing the top-treated soil layer from the seed row to the inter-row area using any tillage, planting, or other technique.

[0186] When the composition of herbicide A is used in a sterilization process, it can be applied before crop sowing (planting) or after sowing (or planting) but before crop emergence.

[0187] In addition to the active ingredient or composition, the agrochemical composition of herbicide A and the formulation of herbicide A also contain at least one organic or inorganic carrier material. The formulation may also contain, if desired, one or more surfactants and, if desired, one or more other adjuvants commonly used in crop protection compositions.

[0188] In the formulation, the active ingredient and optional other active ingredients are present in suspension, emulsion, or dissolved form. The formulation may be in the form of aqueous solution, powder, suspension, as well as highly concentrated aqueous, oil or other suspensions or dispersions, water emulsions, water microemulsions, water suspension emulsions, oil dispersions, pastes, dusts, spreading materials, or granules.

[0189] Depending on the type of formulation, they contain one or more liquid or solid carriers, (if appropriate) surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents, and thickeners), and (if appropriate) other adjuvants commonly used in formulating product protection products. Those skilled in the art are well familiar with the formulation of such formulations. Other adjuvants include, for example, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, colorants, and binders for seed formulations.

[0190] Suitable carriers include liquid and solid carriers. Liquid carriers include, for example, non-aqueous solvents such as cyclic and aromatic hydrocarbons, such as paraffin, tetrahydronaphthalene, alkylnaphthalene and their derivatives, alkylbenzene and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents such as amines such as N-methylpyrrolidone, and water, and mixtures thereof. Solid carriers include, for example, minerals such as silica, silica gel, silicates, talc, kaolin, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and plant-derived products such as grain flour, bark flour, wood flour and nut shell powder, cellulose powder, or other solid carriers.

[0191] Suitable surfactants (auxiliaries, wetting agents, thickeners, dispersants, and emulsifiers) are aromatic sulfonic acids, such as lignin sulfonic acids (e.g., Borrespers type, Borregaard), phenol sulfonic acids, naphthalene sulfonic acids (Morwet type, Akzo Nobel), and dibutylnaphthalene sulfonic acids (Nekal type, BASF). Alkali metal salts, alkaline earth metal salts, and ammonium salts of fatty acids, alkyl sulfonates and alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates, and fatty alcohol sulfates, and salts of sulfated hexa-, hepta-, and octadecyl alcohols, as well as salts of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, octylphenol polyoxyethylene ethers, ethoxylated isooctyl-, octyl-, or nonylphenol, alkylphenyl or tributylphenyl polyethylene glycol ethers, alkyl aryl polyether alcohols, isotriadecyl alcohol, fatty alcohol / ethylene oxide condensates Materials, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl glycol ether acetate, sorbitol esters, lignin sulfite waste liquid and proteins, denatured proteins, polysaccharides (e.g., methylcellulose), hydrophobically modified starch, polyvinyl alcohol (Mowiol type, Clariant), polycarboxylate (BASF, Sokalan type), polyalkoxylates, polyvinylamine (BASF, Lupamine type), polyethyleneimine (BASF, Lupasol type), polyvinylpyrrolidone and its copolymers.

[0192] Examples of thickeners (i.e., compounds that impart improved flow properties to formulations, i.e., compounds that have high viscosity at rest and low viscosity when in motion) are polysaccharides, such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from RTVanderbilt) as well as organic and inorganic platy minerals, such as Attaclay® (from Engelhardt)

[0193] Examples of defoamers are silicone emulsions (such as Silikon). ® SRE, Wacker or Rhodorsil®, from Rhodia, long-chain alcohols, fatty acids, fatty acid salts, organofluorine compounds and mixtures thereof.

[0194] Fungicides can be added to stabilize water-based herbicidal formulations. Examples of fungicides include dichlorophenol and benzyl alcohol hemiformal-based fungicides (Proxel® from ICI, Acticide® RS from Thor Chemie, and Kathon® MK from Rohm & Haas), as well as isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS from Thor Chemie).

[0195] Examples of antifreeze agents are ethylene glycol, propylene glycol, urea, or glycerin.

[0196] Examples of colorants are both slightly water-soluble pigments and water-soluble dyes. Examples that may be mentioned are dyes known by the following names: Rhodamine B, CI Pigment Red 112 and CI Solvent Red 1, as well as Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 112, Pigment Red 48:2, Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet 10, Basic Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10, and Basic Red 108.

[0197] Examples of adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, and methylcellulose (tylose).

[0198] To prepare emulsions, pastes, or oil dispersions, the active ingredient (either as is or dissolved in oil or solvent) can be homogenized in water using a wetting agent, thickener, dispersant, or emulsifier. Alternatively, concentrates consisting of the active substance, wetting agent, thickener, dispersant, or emulsifier, and (if desired) solvent or oil can be prepared, and these concentrates are suitable for dilution with water.

[0199] Powders, spreading materials, and dusts can be prepared by mixing or simultaneously grinding the active ingredients herbicides A and B with a solid carrier.

[0200] Granules, such as coated granules, impregnated granules, and uniform granules, can be prepared by bonding the active ingredient to a solid carrier.

[0201] It may be beneficial to apply herbicide A alone or in combination with other herbicides, or additionally in mixtures with other crop protectants, such as with agents used to control harmful organisms or plant pathogenic fungi or bacteria. Also of interest is its miscibility with mineral salt solutions used to treat nutrient and trace element deficiencies. Other additives such as non-phytotoxic oils and oil concentrates may also be added.

[0202] These formulations contain an effective amount of herbicide A. The concentration of the active ingredient in the formulation can vary over a wide range. Typically, the formulation contains 1% to 98%, preferably 10% to 60% by weight, of the active ingredient (herbicide A and optional other active ingredients). The active ingredient is used at a purity of 90% to 100%, preferably 95% to 100% (based on NMR spectra).

[0203] Herbicide A (i.e., the active compound or composition) can be formulated, for example, as follows:

[0204] Products diluted with water

[0205] A water-soluble concentrate

[0206] Dissolve 10 parts by weight of the active compound (or composition) in 90 parts by weight of water or a water-soluble solvent. Alternatively, a wetting agent or other adjuvant may be added. The active compound is dissolved upon dilution with water. This yields a formulation containing 10% active compound by weight.

[0207] B Dispersible Concentrate

[0208] Dissolve 20 parts by weight of the active compound (or composition) in 70 parts by weight of cyclohexanone, and add 10 parts by weight of a dispersant, such as polyvinylpyrrolidone. Dilute with water to obtain a dispersion. The active compound content is 20% by weight.

[0209] C emulsifiable concentrate

[0210] Dissolve 15 parts by weight of the active compound (or composition) in 75 parts by weight of an organic solvent (e.g., an alkyl aromatic compound), and add calcium dodecylbenzenesulfonate and castor oil ethoxylate (5 parts by weight in each case). Dilute with water to obtain an emulsion. The formulation has an active compound content of 15% by weight.

[0211] D Emulsion

[0212] 25 parts by weight of the active compound (or composition) are dissolved in 35 parts by weight of an organic solvent (e.g., an alkyl aromatic compound), and calcium dodecylbenzenesulfonate and castor oil ethoxylate (5 parts by weight in each case) are added. This mixture is introduced into 30 parts by weight of water using an emulsifier (Ultraturrax) to form a homogeneous emulsion. The emulsion is diluted with water. The formulation has an active compound content of 25% by weight.

[0213] E suspension

[0214] In a stirred ball mill, 20 parts by weight of the active compound (or composition) are pulverized, and 10 parts by weight of a dispersant and wetting agent, along with 70 parts by weight of water or an organic solvent, are added to obtain a fine suspension of the active compound. The suspension is then diluted with water to obtain a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.

[0215] F Water-dispersible granules and water-soluble granules

[0216] 50 parts by weight of the active compound (or composition) are finely ground and 50 parts by weight of a dispersant and a wetting agent are added. The mixture is then processed into water-dispersible or water-soluble granules using advanced equipment such as extrusion, spray towers, or fluidized beds. The granules are diluted with water to obtain a stable dispersion or solution of the active compound. The formulation contains 50% active compound by weight.

[0217] G water-dispersible powder and water-soluble powder

[0218] 75 parts by weight of the active compound (or composition) are milled in a rotor-stator mill, and 25 parts by weight of a dispersant, wetting agent, and silica gel are added. The mixture is diluted with water to obtain a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.

[0219] H gel formulation

[0220] 20 parts by weight of the active compound (or composition), 10 parts by weight of the dispersant, 1 part by weight of the gelling agent, and 70 parts by weight of water or organic solvent are mixed in a ball mill to obtain a fine suspension. The suspension is then diluted with water to obtain a stable suspension containing 20% ​​by weight of the active compound.

[0221] Aqueous forms can be prepared by adding water from emulsion concentrates, suspensions, pastes, wettable powders, or water-dispersible granules.

[0222] Examples of uses

[0223] Biological examples

[0224] The herbicidal activity of compounds having formula (I) was demonstrated through the following greenhouse or field experiments:

[0225] Greenhouse Experiment:

[0226] The culture containers used were plastic flowerpots containing sandy loam soil with approximately 3.0% organic matter as a substrate. Seeds of test plants were sown individually for each species.

[0227] For pre-emergence treatment, after sowing, the active ingredient, already suspended or emulsified in water, is applied directly using a fine-dispensing nozzle. The containers are gently irrigated to promote germination and growth, and then covered with a transparent plastic cover until the test plants have rooted. This covering ensures uniform germination of the test plants, unless they have been damaged by the active ingredient.

[0228] For post-emergence treatment, depending on the plant's habits, test plants are first allowed to grow to a height of 3 to 20 cm, and then treated only with the active ingredient suspended or emulsified in water. For this purpose, test plants are either directly sown and grown in the same container, or they are first grown individually as seedlings and then transplanted into test containers a few days before treatment.

[0229] Depending on the species, the test plants were kept at 10°C-25°C or 20°C-35°C, respectively.

[0230] The testing period lasts 2 to 4 weeks. During this time, the test plants are cared for, and their responses to individual treatments are evaluated.

[0231] Evaluations were conducted using a scale of 0 to 100. 100 indicates no plant emergence, or at least complete destruction of the above-ground portion, while 0 indicates no damage or normal growth. Values ​​of 70 to < 90 were given for good herbicidal activity, and values ​​of 90 to 100 were given for very good herbicidal activity.

[0232] field experiment

[0233] At field test sites, for pre-emergence timing, the area of ​​the field is treated before or shortly after crop sowing, but before the emergence of the crop or weeds. For post-emergence timing, the crop and weeds are treated at the specified growth stage. Therefore, the active ingredient in the specified formulation is suspended or emulsified in water and applied at the appropriate time using finely distributed nozzles.

[0234] Evaluations were conducted using a scale of 0 to 100. 100 indicates no plant emergence, or at least complete destruction of the above-ground portion, while 0 indicates no damage or normal growth. Values ​​of 70 to < 90 were given for good herbicidal activity, and values ​​of 90 to 100 were given for very good herbicidal activity.

[0235] The following active compounds have been tested:

[0236] Compound Ia:

[0237]

[0238] Compound Ib:

[0239]

[0240] Compound Ic:

[0241]

[0242] Compound Id:

[0243]

[0244] Compounds Ia to Id were used as a 5% EC formulation with a water carrier of 375 L / ha and with 0.5% adjuvant (in small amounts).

[0245] The test plants used in the greenhouse / field experiments belong to the following species:

[0246]

[0247] The results of these tests are given below in the examples of use, and confirm the synergistic effect of mixtures containing at least one compound having formula (I) and at least one herbicide B.

[0248] In this context, "ai" refers to the active ingredient, based on 100% active ingredient. Compounds Ia to Id are used as EC formulations with an active ingredient concentration of 100 g / L.

[0249] As indicated, application is carried out after emergence (POST) or before emergence (PRE) at the corresponding growth stage (GS) (BBCH code) of the weed.

[0250] The example indicates the evaluation of Days After Processing (DAT).

[0251] Example 1 - Pre-emergence application (field), transplanted rice, ORYSA applied in BBCH 12-13. 28 DAT assessed for phytotoxicity or efficacy.

[0252] Cyclohexane is used as an EC formulation with an active ingredient concentration of 750 g / L.

[0253]

[0254] Example 2 - Pre-emergence application (field), transplanted rice, ORYSA applied in BBCH 12-13.

[0255] Pendimethalin is used as an EC formulation with an active ingredient concentration of 330 gg / l.

[0256] 28. DAT is used to assess phytotoxicity or efficacy.

[0257]

[0258] Example 3 - Pre-emergence application

[0259] 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridyl]oxy]phenoxy]ethyl acetate is used as an SC formulation with an active ingredient concentration of 342.1 g / l.

[0260] Use water as a carrier and apply it at a ratio of 375 L / ha water volume.

[0261] 20 DAT is used to assess plant toxicity or efficacy.

[0262]

[0263] Example 4 - Pre-emergence application

[0264] Pretilachlor is used as an EW formulation with an active ingredient concentration of 400 g / L.

[0265] In an example of transplanted rice, the herbicide was applied 4 days after transplanting, before weed emergence. Phytotoxicity was given as the maximum value across all assessments.

[0266] 45. DAT efficacy assessment.

[0267]

[0268] Examples of transplanted rice, delayed weed emergence, and application 7 days after transplanting. Phytotoxicity is given as the maximum value in all assessments.

[0269] 42. DAT efficacy assessment.

[0270] .

Claims

1. A method for selectively controlling weeds in rice, the method comprising applying an effective amount of a herbicide mixture to a crop cultivation area, the herbicide comprising herbicide A as component 1), the herbicide A being selected from compounds having formula (I) and salts of compounds having formula (I). (I) in R 1 is F; R 2 selected from the group consisting of H, halogen; R 3 is H, F; R 4 selected from the group consisting of F, CI, Br, I; R 5 selected from the group consisting of H, halogen and Ci-C6-alkyl; R 6 is selected from the group consisting of H, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy; R 7 is selected from the group consisting of H, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy; R 8 Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl; and As component 2), at least one other compound selected from compound B: B1) Selected from the group of lipid biosynthesis inhibitors: cyhalofop-butyl, cyclobenzanone, fenvalerate, and clodinafop-propargyl; B2) Group selected from ALS inhibitors: bispyribac-sodium, bensulfuron-methyl, ethoxysulfuron, methyl imazalil, imazalilnic acid, imazalil, promethazine, pyrimisulfuron, fluazinam; B3) Selected from the photosynthesis inhibitor group: atrazine, cyclomethanone, cypermethrin, diuron, thiamethoxam and thiamethoxam-sodium; B4) Selected from the group of protoporphyrinogen-IX oxidase inhibitors: flupyrimichlor, propyzoxyl, bispyribac-methyl, pyrimisulfuron-methyl, trifluralin, 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridyl]oxy]phenoxy]ethyl acetate (CAS 2158274-50-9); B5) Selected from the group of bleaching herbicides: PDS inhibitors: flubutyrazole, dichlorvos, pyrfluthrin, flupyrfluthrin, flurfluthrin, furazolidone, dapoxetine, flupyrfluthrin, 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33-7), limexafine; HPPD inhibitors: bicyclosulfuron, isoxaflutole, mesosulfuron, cyclosulfuron, pyridinesulfuron, benzoxazine. B6) Group from EPSP synthase inhibitors: Glyphosate, glyphosate-isopropylammonium, glyphosate-potassium and glyphosate-trimethyl sulfide (thiophos); B7) Group from glutamine synthase inhibitors: Glufosinate, granulated glufosinate, glufosinate-ammonium and granulated glufosinate-ammonium. B9) Selected from the group containing mitosis inhibitors: Compounds in group K1: pendimethalin, trifluralin, and isoxaflutamide methyl ester; B10) Selected from the VLCFA inhibitor group: Butachlor, S-methylphenidate, S-metolachlor, propachlor, sulfonylpyrazosulfuron; c13) Selected from the group of plant growth regulator herbicides: 2,4-D and its salts and esters, such as chlorpyrifos, 2,4-DB and its salts and esters, dicamba and its salts and esters, and chlorpyrifos. B15) Selected from other herbicides: bromobutyroxyfen, chlorpyrifos, cyclohexane, tetraflufenoxam.

2. The method of claim 1, wherein, Herbicide A is selected from compounds having formula (I), wherein, R 1 is F; R 2 is halogen; R 3 is H, F; R 4 Choose the group composed of F, Cl, Br, and I; R 5 is halogen; R 6 is Ci-C6-alkyl; R 7 is Ci-C6-alkyl; R 8 is C1-C6-alkyl.

3. The method of claim 1 or 2, wherein, Herbicide A is selected from compounds Ia to Id: Compound Ia: Compound Ib: Compound Ic: Compound Id:

4. The method of any one of claims 1 to 3, wherein, Component 2) is selected from the following compound B: Cyfluthrin, Cyclobutrazol; Benzylsulfuron-methyl, bispyribac-sodium, ethoxysulfuron, promethazine-sulfuron, pyrimisulfuron; Thiamethoxam and thiamethoxam-sodium; Bismuth subtilis and pyrimethanil; Bicyclosulfuron; Aldex; Butachlor and pretilachlor; chloropyridine benzyl ester; Cyclohexane and tetraflufenican.

5. The method according to any one of claims 1 to 4, wherein, Apply it before or after the crop emerges, until the crop reaches growth stage 29-37.

6. The method of any one of claims 1 to 5, wherein, Apply herbicide A until the weed reaches growth stage 37.

7. The method of any one of claims 1 to 6, wherein, The ratio of herbicide A to herbicide B in the mixture is 8:1 to 1:

500.

8. The method of any one of claims 1 to 7, wherein, The ratio of herbicide A to herbicide B in the mixture is 2:1 to 1:

200.

9. The method of any one of claims 1 to 8, wherein, The ratio of herbicide A to herbicide B in the mixture is 1:1 to 1:

100.

10. The method according to any one of claims 1 to 8, wherein, The ratio of herbicide A to herbicide B in the mixture is 1:1 to 1:

75.

11. The method of claim 10, wherein, These weed species were selected from the following groups: - Dicotyledonous species: *Amaranthus dentata*, *Abutilon theophrasti*, *Alternanthera philoxeroides*, *Amaranthus longissimus*, *Amaranthus retroflexus*, *Amaranthus rubrotinctum*, *Amaranthus rubrotinctum*, *Amaranthus rubrotinctum*, *Amaranthus multiflora*, *Eclipta prostrata*, *Symplocos rubrotinctum*, *Symplocos rubrotinctum*, *Symplocos rubrotinctum*, *Polygonum hydropiper*, *Charachium chinense*, *Platycodon grandiflorus*, *Pterocarya stenoptera*; - Monocotyledonous species (especially the following sedges): Cyperus difformis, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus, Cyperus rotundus; - Monocotyledonous species (especially the following grasses): Bermuda grass, Imperata cylindrica, Barnyard grass, Bald barnyard grass, Goosegrass, Field duckweed, Fine-leaved clematis, Fine-spike clematis, Cressidae, Lespedeza bicolor, Paspalum notatum; - Monocotyledonous species (excluding grasses or sedges): Narrow-leaved water plantain, yellow iris, raindrop, duckweed, pondweed.

12. The method of any one of claims 1 to 11, wherein, Apply the herbicide mixture once, twice, or three times until the crop is harvested, preferably once until the crop is harvested.

13. A composition comprising the herbicidal mixture according to claims 1 to 12 and at least one adjuvant commonly used in the formulation of crop protection compounds.

14. The composition of claim 13, wherein the composition comprises an additional herbicide.

15. Use of the herbicidal mixture according to claims 1 to 12 or the composition according to claim 13 or 14 for selective control of weeds in rice.

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