# Patent

## Title
Synergistically acting herbicidal mixtures

## Abstract

A synergistic herbicidal mixture comprising

    A) at least one 3-heterocyclyl-substituted benzoyl derivative of the formula I






in which the variables have the following meanings:

    
    
        R1, R3 are halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl;
        R2 is a optionally substituted heterocyclic radical selected from the group: isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl and 4,5-dihydroisoxazol-5-yl;
        R4 is hydrogen, halogen or alkyl;
        R5 is alkyl;
        R6 is hydrogen or alkyl;
        or one of its environmentally compatible salts;

and

    
    
    B) a synergistically effective amount of the compound of formula II






    
    
        or one of its environmentally compatible salts;

and, if desired,

    
    
    C) at least one further herbicidal compound;

and, if desired,

    D) at least a safener.


Compositions comprising these mixtures, processes for the preparation of these compositions, and their use for controlling undesired plants.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application is a 35 USC §371 National Phase Entry Application from PCT/EP2003/007321, filed Jul. 8, 2003, and designating the U.S., which claims the priority of U.S. Provisional Application No. 60/393,740 filed Jul. 8, 2002.


The present invention relates to a synergistic herbicidal mixture comprising

    A) at least one 3-heterocyclyl-substituted benzoyl derivative of the formula I






    
    
        in which the variables have the following meanings:
        R1, R3 are halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl or C1-C6-alkylsulfonyl;
        R2 is a heterocyclic radical selected from the group: isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl and 4,5-dihydroisoxazol-5-yl, it being possible for the six radicals mentioned to be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio;
        R4 is hydrogen, halogen or C1-C6-alkyl;
        R5 is C1-C6-alkyl;
        R6 is hydrogen or C1-C6-alkyl;
        or one of its environmentally compatible salts;

and

    
    
    B) a synergistically effective amount of the compound of formula II






    
    
        or one of its environmentally compatible salts;

and, if desired,

    
    
    C) at least one herbicidal compound from the group of the acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, enolpyruvylshikimate 3-phosphate synthase inhibitors (EPSPS)—, glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporphyrinogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth substances, cell wall biosynthesis inhibitors and a variety of other herbicides;

and, if desired,

    D) a safening effective amount of at least one safener selected from the group of isoxadifen, mefenpyr and fenchlorazol;
    
        or one of its environmentally compatible salts or esters.
    
    


The invention furthermore relates to herbicidal compositions comprising a herbicidally active amount of a synergistic herbicidal mixture as defined above and at least one liquid and/or solid carrier and, if desired, at least one surfactant.
Moreover, the invention relates to processes for the preparation of these compositions and to a method of controlling undesirable vegetation.
In crop protection products, it is always desirable to increase the specific activity of an active ingredient and the reliability of action. It is an object of the present invention to increase the activity and/or selectivity of the herbicidally active 3-heterocyclyl-substituted benzoyl derivatives of the formula I against undesirable harmful plants.
We have found that this object is achieved by the mixtures defined at the outset. We have furthermore found herbicidal compositions which comprise these mixtures, processes for their preparation, and methods of controlling undesirable vegetation. In the last-mentioned cases, it is irrelevant whether the herbicidally active compounds of the components A), B) and, if desired, C) and, if desired, D) are formulated and applied jointly or separately and in which sequence they are applied in the case of separate application.
The mixtures according to the invention show a synergistic effect; the compatibility of the herbicidally active compounds of components A), B) and, if desired, C) for certain crop plants is generally retained.
Suitable components C are, as acetyl-CoA carboxylase inhibitors (ACC), for example, cyclohexenone oxime ethers, phenoxyphenoxy-propionic esters or arylaminopropionic acids. The acetolactate synthase inhibitors (ALS) include, inter alia, imidazolinones, pyrimidyl ethers, sulfonamides or sulfonyl ureas. Relevant auxin herbicides are, inter alia, pyridine carboxylic-acids, 2,4-D or benazolin. Lipid biosynthesis inhibitors which are used are, inter alia, anilides, chloroacetanilides, thioureas, benfuresate or perfluidone. Suitable mitosis inhibitors are, inter alia, carbamates, dinitroanilines, pyridines, butamifos, chlorthal-dimethyl (DCPA) or maleic hydrazide. Examples of protoporphyrinogen IX oxidase inhibitors are, inter alia, diphenyl ethers, oxadiazoles, cyclic imides or pyrazoles. Suitable photosynthesis inhibitors are, inter alia, propanil, pyridate, pyridafol, benzothiadiazinones, dinitrophenols, dipyridylenes, ureas, phenols, chloridazon, triazine, triazinone, uracils or biscarbamates. The synergists are, inter alia, oxiranes. Examples of suitable growth substances are aryloxyalkanoic acids, benzoic acids or quinolinecarboxylic acids. The group “various other herbicide” is to be understood as meaning, inter alia, the classes of the active ingredients dicloropropionic acids, dihydrobenzofurans, phenylacetic acids and individual herbicides mentioned below whose mechanism of action is not (fully) understood.
Other suitable components C are active compounds selected from the group of the amides, auxin transport inhibitors, carotenoic biosynthesis inhibitors, enolpyruvylshikimate 3-phosphate synthase inhibitors (EPSPS), glutamine synthetase inhibitors and cell wall synthesis inhibitors.
Examples of herbicides which can be used in combination with the 3-heterocyclyl-substituted benzoyl derivatives of formula I and the compound of formula II according to the present invention are, inter alia:
C1 acetyl-CoA carboxylase inhibitors (ACC), for example


    
    
        cyclohexenone oxime ethers, such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, butroxydim, clefoxydim or tepraloxydim;
        phenoxyphenoxypropionic esters, such as clodinafop-propargyl (and, if appropriate, cloquintocet), cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-P-ethyl or quizalofop-tefuryl; or
        arylaminopropionic acids, such as flamprop-methyl or flamprop-isopropyl;

C2 acetolactate synthase inhibitors (ALS), for example

        imidazolinones, such as imazapyr, imazaquin, imazamethabenz-methyl (imazame), imazamoc, imazapic, imazethapyr or imazamethapyr;
        pyrimidyl ethers, such as pyrithiobac-acid, pyrithiobac-sodium, bispyribac-sodium, K1H-6127 or pyribenzoxym;
        sulfonamides, such as florasulam, flumetsulam or metosulam; or
        sulfonylureas, such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]carbonyl]-2-(trifluoro-methyl)-benzenesulfonamide, sulfosulfuron or iodosulfuron;

C3 amides, for example

        allidochlor (CDAA), benzoylprop-ethyl, bromobutide, chlorthiamid, diphenamid, etobenzanid (benzchlomet), fluthiamide, fosamin or monalide;

C4 auxin herbicides, for example

        pyridinecarboxylic acids, such as clopyralid or picloram; or
        2,4-D or benazolin;

C5 auxin transport inhibitors, for example

        naptalame or diflufenzopyr;

C6 carotenoid biosynthesis inhibitors, for example

        benzofenap, clomazone (dimethazone), diflufenican, fluorochloridone, fluridone, pyrazolynate, pyrazoxyfen, isoxaflutole, isoxachlortole, mesotrione, sulcotrione (chlormesulone), ketospiradox, flurtamone, norflurazon or amitrol;

C7 enolpyruvylshikimate-3-phosphate synthase inhibitors (EPSPS), for example

        glyphosate or sulfosate;

C8 glutamine synthetase inhibitors, for example

        bilanafos (bialaphos) or glufosinate-ammonium;

C9 lipid biosynthesis inhibitors, for example

        anilides, such as anilofos or mefenacet;
        chloroacetanilides, such as dimethenamid, S-dimethenamid, acetochlor, alachlor, butachlor, butenachlor, diethatyl-ethyl, dimethachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor or xylachlor;
        thioureas, such as butylate, cycloate, di-allate, dimepiperate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb (benthiocarb), tri-allate or vernolate; or
        benfuresate or perfluidone;

C10 mitosis inhibitors, for example

        carbamates, such as asulam, carbetamid, chlorpropham, orbencarb, pronamid (propyzamid), propham or tiocarbazil;
        dinitroanilines, such as benefin, butralin, dinitramin,
        ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine or trifluralin;
    
    


pyridines, such as dithiopyr or thiazopyr; or

    
    
        butamifos, chlorthal-dimethyl (DCPA) or maleic hydrazide;

C11 protoporphyrinogen IX oxidase inhibitors, for example

        diphenyl ethers, such as acifluorfen, acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP), ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen or oxyfluorfen;
        oxadiazoles, such as oxadiargyl or oxadiazon;
        cyclic imides, such as azafenidin, butafenacil, carfentrazone-ethyl, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, sulfentrazone or thidiazimin; or
        pyrazoles, such as ET-751, JV 485 or nipyraclofen;

C12 photosynthesis inhibitors, for example

        propanil, pyridate or pyridafol;
        benzothiadiazinones, such as bentazone;
        dinitrophenols, for example bromofenoxim, dinoseb, dinoseb-acetate, dinoterb or DNOC;
        dipyridylenes, such as cyperquat-chloride, difenzoquat-methylsulfate, diquat or paraquatt-dichloride;
        ureas, such as chlorbromuron, chlorotoluron, difenoxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, methazole, metobenzuron, metoxuron, monolinuron, neburon, siduron or tebuthiuron;
        phenols, such as bromoxynil or ioxynil;
        chloridazon;
        triazines, such as ametryn, atrazine, cyanazine, desmetryn, dimethamethryn, hexazinone, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbutylazine or trietazine;
        triazinones, such as metamitron or metribuzin;
        uracils, such as bromacil, lenacil, or terbacil; or
        biscarbamates, such as desmedipham or phenmedipham;

C13 synergists, for example

        oxiranes, such as tridiphane;

C14 growth substances, for example

        aryloxyalkanoic acids, such as 2,4-DB, clomeprop, dichlorprop, dichlorprop-P (2,4-DP-P), fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P or triclopyr;
        benzoic acids, such as chloramben or dicamba; or
        quinolinecarboxylic acids, such as quinclorac or quinmerac;

C15 cell wall synthesis inhibitors, for example

        isoxaben or dichlobenil;

C16 various other herbicides, for example

        dichloropropionic acids, such as dalapon;
        dihydrobenzofurans, such as ethofumesate;
        phenylacetic acids, such as chlorfenac (fenac); or
        aziprotryn, barban, bensulide, benzthiazuron, benzo-fluor, buminafos, buthidazole, buturon, cafenstrole, chlorbufam, chlorfenprop-methyl, chloroxuron, cin-methylin, cumyluron, cycluron, cyprazine, cyprazole, dibenzyluron, dipropetryn, dymron, eglinazin-ethyl, endothall, ethiozin, flucabazone, fluorbentranil, flupoxam, isocarbamid, isopropalin, karbutilate, mefluidide, monuron, napropamide, napropanilide, nitralin, oxaciclomefone, phenisopham, piperophos, procyazine, profluralin, pyributicarb, secbumeton, suifallate (CDEC), terbucarb, triaziflam, triazofenamid or trimeturon;
    
    


or their environmentally compatible salts.
The 3-heterocyclyl-substituted benzoyl derivatives of the formula I are disclosed in WO 96/26206, WO 97/41116, WO 97/41117 and WO 97/41118, WO 98/31681.
The compound of formula II (common name foramsulfuron) is disclosed in U.S. Pat. No. 5,922,646.
The herbicidally active compounds from amongst groups C1 to C16 are described, for example, in

    
    
        “Herbizide [Herbicides]”, Hock, Fedtke, Schmidt, 1st edition, Thieme 1995 (s. “quinclorac” p. 238, “molinat” p. 32, “butachlor” p. 32, “pretilachlor” p. 32, “dithiopyr” p. 32, “mefenacet” p. 32, “fenoxapropethyl” p. 216, “dimepiperate” p. 32, “pyrazolynate” p. 146, “pyrazoxyfen” p. 146, “bensulfuronmethyl” p. 31, “pyrazosulfuron-ethyl” p. 31, “cinosulfuron” p. 31, “benfuresate” p. 233, “bromobutide”p. 243, “dymron” p. 243, “dimethyametryn” p. 118, “esprocarb” p. 229, “pyributicarb” p. 32, “cinemthylin” p. 32, “propanil” p. 32, “2,4-D” p. 30, “bentazon” p. 30, “azimsulfuron (DPX-A-8947)” p 175, “mecoprop-P” p. 237, “chlorpropham” p. 205, “ethoxyfen” p. 30, “haloxyfop-P-methyl” p. 38, “haloxyfop-ethoxyethyl” p. 38, “flumiclorac-pentyl” p. 35, “flupropacil” p. 143, “nipyraclofen” p. 145, “metosulam” p. 33, “ethametsulfuron-methyl” p. 36, “thifensulfuron-methyl” p. 35, “pyrithiobac acid” p. 181);
        “Agricultural Chemicals”, Book II Herbicides, 1993 (s. “thiobencarb” p. 85, “benzofenap” p. 221, “napropanilid” p. 49, “piperophos” p. 102, “anilofos” p. 241, “imazosulfuron (TH-913)” p. 150, “etobenzamid (HW-52)” p. 54, “sulcotrione (ICIA-0051)” p. 268, “poast” p. 253, “focus” p. 222, “dimethenamid” p. 48, “sulfosate” p. 236, “2,4-DB” p. 10, “dichlorprop-P” p. 6, “flupoxam” p. 44, “prosulfocarb” p. 84, “quinmerac” p. 233, “metazachlor” p. 64, “flurtamone” p. 265, “bromofenoxim” p. 228, “fomesafen” p. 248, “imazamethabenz-methyl” p. 153, “clodinafop-propargyl” p. 214, “fenoxaprop-P-ethyl” p. 208, “fluazifop-P-butyl” p. 207, “quizalofop-P-ethyl” p. 210, “quizalofop-terfuryl” p. 211, “flumioxazin” p. 43, “flumipropyn” p. 267, “sulfentrazone” p. 261, “thiazopyr” p. 226, “pyrithiobac-sodium” p. 266, “flumetsulam” p. 227, “amidosulfuron” p. 151, “halosulfuron-methyl” p. 148, “rimsulfuron” p. 138, “tribenuron-methyl” p. 139, “triflusulfuron-methyl” p. 137, “primisulfuron-methyl” p. 147);
        “Agricultural Chemicals”, Book II Herbicides, 13th Edition (s. “carfenstole” p. 284, “sulfosulfuron” p. 145, “ethoxy-sulfuron” p. 149, “pyribenzoxym” p. 279, “diflufenzopyr” p. 90, “ET-751” p. 278, “carfentrazone-ethyl” p. 267, “fluthiacet-methyl” p. 277, “imazapic” p. 160, “butenachlor” p. 54, “tiocarbazil” p. 84, “fluthiamide” p. 62, “isoxa-flutole” p. 283, “butroxydim” p. 259,);
        “Short Review of Herbicides & PGRs 1991, Hodogaya Chemicals (s. “furyloxyfen” p. 142, “triazofenamid” p. 268, “thenylchlorid (NSK-850)” p. 52, “cumyluron (JC-940)” p. 90, “pendimethalin (AC-92553)” p. 58, “buthidazole” p. 88, “cyprazole” p. 38, “allidochlor” p. 48, “benzoylprop-ethyl” p. 38, “chlorthiamid” p. 150, “diphenamid” p. 34, “flamprop-methyl” p. 40, “fosamin” p. 232, “isoxaben” p. 42, “monalide” p. 32, “naptalam” p. 36, “pronamid” p. 34, “bialaphos” p. 234, “glufosinate-ammonium” p. 234, “glyphosate” p. 232, “amitrol” p. 254, “clomeprop p. 20, “dichlorprop” p. 6, “fenoprop” p. 8, “fluroxypyr” p. 156, “MCPA” p. 4, “MCPB” p. 8, “mecoprop” p. 6, “napropamide” p. 16, “triclopyr” p. 154, “chloramben” p. 28, “dicamba” p. 26, “clomazone” p. 268, “diflufenican” p. 42, “fluorochloridone” p. 266, “fluridone” p. 156, “asulam” p. 112, “barban” p. 100, “butylate” p. 106, “carbetamide” p. 36, “chlorobufam” p. 100, “cycloate” p. 108, “desmedipham” p. 104, “di-allate” p. 106, “EPTC” p. 108, “orbencarb” p. 112, “pebulate” p. 106, “phen-isopham” p. 118, “phenmedipham” p. 104, “propham” p. 100, “sulfallate” p. 110, “terbucarb” p. 102, “tri-allate” p. 108, “vernolate” p. 108, “acetochlor” p. 48, “alachlor” p. 46, “diethathyl-ethyl” p. 48, “dimethachlor” p. 50, “metolachlor” p. 46, “propachlor” p. 44, “pyrnachlor” p. 44, “terbuchlor” p. 48, “xylachlor” p. 52, “alloxydim” p. 260, “clethodim” p. 270, “cloproxydim” p. 268, “tralkoxydim” p. 270, “dalapon” p. 212, “ethofumesate” p. 124, “benefin” p. 54, “butralin” p. 58, “dinitramin” p. 56, “ethalfluralin” p. 60, “fluchloralin” p. 54, “isopropalin” p. 58, “nitralin” p. 58, “oryzalin” p. 60, “prodiamine” p. 62, “profluralin” p. 54, “trifluralin” p. 54, “dinoseb” p. 128, “dinoseb-acetate” p. 128, “dinoterb” p. 128, “DNOC” p. 126, “acifluorfen-sodium” p. 142, “aclonifen” p. 146, “bifenox” p. 140, “chlornitrofen” p. 138, “difenoxuron” p. 76, “fluorodifen” p. 138, “fluoroglycofen-ethyl” p. 146, “lactofen” p. 144, “nitrofen” p. 136, “nitrofluorfen” p. 140, “oxyfluorfen” p. 140, “cyperquat-chloride” p. 158, “difenzoquat-methylsulfate” p. 160, “diquat” p. 158, “paraquat-dichloride” p. 158, “benzthi-azuron” p. 82, “buturon” p. 66, “chlorbromuron” p. 72, “chloroxuron” p. 76, “chlorotoluron” p. 74, “cycluron” p. 84, “dimefuron” p. 88, “diuron” p. 70, “ethidimuron” p. 86, “fenuron” p. 64, “fluometuron” p. 68, “isoproturon” p. 80, “isouron” p. 88, “karbutilate” p. 76, “linuron” p. 72, “methabenzthiazuron” p. 82, “metoxuron” p. 72, “monolinuron” p. 66, “monuron” p. 64, “neburon” p. 72, “siduron” p. 68, “tebuthiuron” p. 86, “trimeturon” p. 64, “isocarbamid” p. 168, “imazamethapyr” p. 172, “imazapyr” p. 170, “imaza-quin” p. 170, “imazethapyr” p. 172, “methazole” p. 162, “oxadiazon” p. 162, “tridiphane” p. 266, “bromoxynil” p. 148, nioxynil” p. 148, “diclofop-methyl” p. 16, “fenthiaprop-ethyl” p. 20, “fluazifop-butyl” p. 18, “haloxyfop-methyl” p. 18, “isoxapyrifop” p. 22, “propaquizafop” p. 24, “quizalo-fop-ethyl” p. 20, “chlorfenac” p. 258, “chlorfenprop-methyl” p. 258, “chloridazong p. 174, “maleic hydrazide” p. 162, “norflurazon” p. 174, “pyridate” p. 176, “clopyralid” p. 154, “picloram” p. 154, “chlorimuron-ethyl” p. 92, “chlorsulfuron” p. 92, “flazasulfuron” p. 96, “metsulfuron-methyl” S.92, “nicosulfuron” p. 96, “sulfometuron-methyl” p. 92, “tria-sulfuron” p. 94, “ametryn” p. 198, “atrazine” p. 188, “aziprotryne” p. 206, “cyanazine” p. 192, “cyprazine” p. 192, “desmetryne” p. 200, “dipropetryn” p. 202, “eglinazine-ethyl” p. 208, “hexazinone” p. 208, “procyazine” p. 192, “prometone” p. 196, “prometryn” p. 196, “propazine” p. 188, “secbumeton” p. 196, “simazine” p. 188, “simetryn” p. 196, “terbumeton” p. 204, “terbutryn” p. 198, “terbutylazine” p. 190, “trietazine” p. 188, “ethiozine” p. 210, “metamitron” p. 206, “metribuzin” p. 202, “bromacil” p. 180, “lenacil” p. 180, “terbacil” p. 180, “benazolin” p. 262, “bensulide” p. 228, “benzofluor” p. 266, “butamifos.” p. 228, “DCPA” p. 28, “dichlobenil” p. 148, “endothal” p. 264, “mefluidide” p. 306, “perfluidone” p. 260, “terbuchlor” p. 48);
        “Global Herbicide Directory” First Edition, 1994 (s. “oxadi-argyl” p. 96);
        “European Directory of Agrochemical Products” Volume 2-Herbicides” Fourth Edition, (s. “buminafos” p. 255).
    
    


Moreover, the compound “DEH-112” is disclosed in European Patent Application EP-A 302 203. The compound “tepraloxydim” is described in DE-A 33 36 140; the compound “cinidon-ethyl” in DE-A 36 03 789 and the compound “fluorbentranil” in EP-A 84 893. Other compounds are known from “Brighton Crop Protection Conference—Weeds—1993” (S. “thidiazimin” p. 29, “AC-322140” p. 41, “KIE-6127” p. 47, “prosulfuron” p. 53, “K1H-2023” p. 61, “metobenzuron” p. 67). The compound “carfenstrole (CH-900)” is mentioned in EP-A 332 133, and the compound N-[[[4-methoxy-6-(trifluoro-methyl)-1,3,5-triazin-2-yl]amino]-carbonyl]-2-(trifluoromethyl-benzenesulfonamide) is described in PCT/EP 96/03996.
The assignment of the active ingredients to the respective mechanisms of action is based on current knowledge. If several mechanisms of action apply to one active ingredient, this substance was only assigned to one mode of action.
The above mentioned safeners (component D) are described, for example, in “Herbizide [Herbicides]” Hock, Fedtke, Schmidt, 1st edition, Thieme 1995 (“fenchlorazol” p. 266), WO 91/07874 (“mefenpyr”) and WO 95/07897 (“isoxadifen”).
The 3-heterocyclyl-substituted benzoyl derivatives of the formula I can exist, or be used, in the form of the pure enantiomers and also as racemates or diastereomer mixtures.
The 3-heterocyclyl-substituted benzoyl derivatives of the formula I and/or the compound of formula II and/or the herbicidally active compounds from amoungs groups C1 to C16 and/or the safeners may also exist in the form of their environmentally compatible salts. Suitable salts are, in general, the salts of those cations, or the acid addition salts of those acids, whose cations, or anions, respectively, do not adversely affect the herbicidal action of the active ingredients.
Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, it being possible in this case, if desired, for one to four hydrogen atoms to be replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C3-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-yl ammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium and sulfoxonium ions, preferably, tri(C1-C4-alkyl)sulfoxonium.
Anions of suitable acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
The safeners may also exist in form of their environmentally compatible esters. Suitable esters are alkyl-, alkoxyalkyl-, allyl-, propargyl- and oxetan-3-ylesters, preferably C1-C10 alkylesters, for example methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, pentyl-, mexyl-(1-ethyl-hexyl-) or isooctyl-(2-ethylhexyl-)esters, C1-C4-alkoxyethylesters, for example methoxyethyl-, ethoxyethyl- or butoxyethylesters, allylesters, propargylesters and oxetan-3-ylesters.
As a rule the ethyl esters of isoxadifen, mefenpyr and fenchlorazol are preferred.
Preferred with regard to the synergistic herbicidal action of the mixtures according to the invention are those 3-heterocyclyl-substituted benzoyl derivatives of the formula I in which the variables have the following meanings, either alone or in combination:

    R1 halogen such as chlorine or bromine, C1-C6-alkyl such as methyl or ethyl or C1-C6-alkylsulfonyl such as methylsulfonyl or ethylsulfonyl; especially preferably chlorine, methyl or methylsulfonyl;
    R2 a heterocyclic radical selected from the group: isoxazol-3-yl, isoxazol-5-yl and 4,5-dihydroisoxazol-3-yl, it being possible for the three radicals mentioned to be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio; especially preferably isoxazol-5-yl, 3-methyl-isoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 5-methyl-4,5-dihydroisoxazol-yl, 5-S ethyl-4,5-dihydroisoxazol-3-yl or 4,5-dimethyl-4,5-dihydroisoxazol-3-yl;
    R3 halogen such as chlorine or bromine or C1-C6-alkylsulfonyl such as methylsulfonyl or ethylsulfonyl; especially preferably chlorine, methylsulfonyl or ethylsulfonyl; R4 hydrogen or methyl; especially preferably hydrogen;
    R5 is C1-C6-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl or 2-methylpropyl; especially preferably methyl, ethyl or 1-methylethyl;
    R6 hydrogen or C1-C6-alkyl, such as methyl or ethyl; especially preferably hydrogen or methyl.


Very particularly preferred are those 3-heterocyclyl-substituted benzoyl derivatives of the formula Ia, in particular the compounds Ia.1 to Ia.47, which are mentioned in Table 1 which








TABLE 1








I








 













No.
R1
R2
R3
R4
R5
R6





Ia.1
Cl
4,5-dihydroisoxazol-3-yl
SO2CH3
H
CH3
CH3


Ia.2
Cl
4,5-dihydroisoxazol-3-yl
Cl
H
CH3
CH3


Ia.3
Cl
4,5-dihydroisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.4
Cl
4,5-dihydro-5-methylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.5
Cl
4,5-dihydro-5,5-dimethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.6
Cl
4,5-dihydro-5-ethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.7
Cl
4,5-dihydro-5,5-diethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.8
Cl
4,5-dihydro-5-chloromethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.9
Cl
4,5-dihydro-5-ethoxyisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.10
Cl
4,5-dihydro-5-methoxyisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.11
Cl
4,5-dihydro-4,5-dimethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.12
Cl
4,5-dihydro-5-thioethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.13
Cl
4,5-dihydro-5-trifluoromethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.14
Cl
4,5-dihydroisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.15
Cl
4,5-dihydroisoxazol-3-yl
Cl
H
C2H5
H


Ia.16
Cl
4,5-dihydro-5-methylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.17
Cl
4,5-dihydro-5,5-dimethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.18
Cl
4,5-dihydro-5-ethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.19
Cl
4,5-dihydro-5,5-diethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.20
Cl
4,5-dihydro-5-chloromethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.21
Cl
4,5-dihydroisoxazol-3-yl
SOCH3
H
C2H5
H


Ia.22
Cl
4,5-dihydro-5-ethoxyisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.23
Cl
4,5-dihydro-4,5-dimethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.24
Cl
4,5-dihydro-5-thioethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.25
Cl
4,5-dihydro-5-trifluoromethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.26
Cl
4,5-dihydroisoxazol-3-yl
SO2CH3
H
i-C4H9
H


Ia.27
CH3
4,5-dihydroisoxazol-3-yl
SO2CH3
H
CH3
CH3


Ia.28
CH3
4,5-dihydroisoxazol-3-yl
Cl
H
CH3
CH3


Ia.29
CH3
4,5-dihydroisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.30
CH3
4,5-dihydro-5-methylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.31
CH3
4,5-dihydro-5,5-dimethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.32
CH3
4,5-dihydro-5-ethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.33
CH3
4,5-dihydro-5,5-diethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.34
CH3
4,5-dihydroisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.35
CH3
4,5-dihydro-4,5-dimethylisoxazol-3-yl
SO2CH3
H
CH3
H


Ia.36
CH3
4,5-dihydroisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.37
CH3
4,5-dihydroisoxazol-3-yl
Cl
H
C2H5
H


Ia.38
CH3
4,5-dihydro-5-methylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.39
CH3
4,5-dihydro-5,5-dimethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.40
CH3
4,5-dihydro-5-ethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.41
CH3
4,5-dihydro-5,5-diethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.42
CH3
4,5-dihydro-4,5-dimethylisoxazol-3-yl
SO2CH3
H
C2H5
H


Ia.43
CH3
4,5-dihydroisoxazol-3-yl
SO2CH3
H
i-C4H9
H


Ia.44
Cl
3-methylisoxazol-5-yl
SO2CH3
H
CH3
H


Ia.45
Cl
3-methylisoxazol-5-yl
SO2CH3
H
C2H5
H


Ia.46
CH3
3-methylisoxazol-5-yl
SO2CH3
H
CH3
H


Ia.47
CH3
3-methylisoxazol-5-yl
SO2CH3
H
C2H5
H









Also very particularly preferred are the compounds Ib, in particular the compounds Ib.1 to Ib.47, which differ from the compounds Ia.1 to Ia.47 only by the fact that they are present as the sodium salt:




Also very particularly preferred are the compounds Ic, in particular the compounds Ic.1 to Ic.47, which differ from the compounds Ia.1 to Ia.47 only by the fact that they are present as the lithium salt:




Also very particularly preferred are the compounds Id, in particular the compounds Id.1 to Id.47, which differ from the compounds Ia.1 to Ia.47 only by the fact that they are present as the potassium salt:




Also very particularly preferred are the compounds Ie, in particular the compounds Ie.1 to Ie.47, which differ from the compounds Ia.1 to Ia.47 only by the fact that they are present as the ammonium salt:




Very particularly preferred are, especially, the compounds Ia, especially the compounds Ia.1 to Ia.47.
Very particularly preferred are, moreover, the 3-heterocyclyl-substituted benzoyl derivatives of the formula I, where

    
    
        R4 is hydrogen.
    
    


Very particularly preferred are, moreover, the 3-heterocyclyl substituted benzoyl derivatives of the formula I where

    
    
        R2 is a heterocyclic radical selected from the group: isoxazol-3-yl, isoxazol-4-yl and isoxazol-5-yl, it being possible for the three radicals mentioned to be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio.
    
    


Very particularly preferred are, especially, the 3-heterocyclyl-substituted benzoyl derivatives of the formula I, where

    
    
        R2 is isoxazol-3-yl which can be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio;
        R4 is hydrogen.
    
    


Very particularly preferred are also, especially, the 3-heterocyclyl-substituted benzoyl derivatives of the formula I where

    
    
        R2 is isoxazol-5-yl, which can be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio;
        R4 is hydrogen.
    
    


Most particularly preferred is 4-[2-chloro-3-(3-methyl-isoxazol-5-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole.
Most particularly preferred is also 4-[2-methyl-3-(3-methyl-isoxazol-5-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole.
Very particularly preferred are, moreover, the 3-heterocyclyl-substituted benzoyl derivatives of the formula I where

    
    
        R2 is a heterocyclic radical selected from the group: 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl and 4,5-dihydroisoxazol-5-yl, it being possible for the three radicals mentioned to be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio.
    
    


Very particularly preferred are, especially, the 3-heterocyclyl-substituted benzoyl derivatives of the formula I where

    
    
        R2 is 4,5-dihydroisoxazol-3-yl which can be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio;
        R4 is hydrogen.
    
    


Most particularly preferred are the 3-heterocyclyl-substituted benzoyl derivatives of the formula I where

    
    
        R1 is halogen or C1-C6-alkyl; and
        R2 is 4,5-dihydroisoxazol-3-yl which can be unsubstituted or mono- or polysubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-alkylthio;
        R3 is C1-C6-alkylsulfonyl;
        R4 is hydrogen.
    
    


Most especially preferred is −4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-methyl-5-hydroxy-1H-pyrazole.
Most particularly preferred is also 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole.
In a further particular embodiment, the synergistic herbicidal mixture comprises, two herbicidal active compounds, a compound of formula I (component A) and the compound of formula II (component B).
For particular preferred embodiments, the respective preferences described above apply analogously.
In particular the synergistic herbicidal mixture comprises as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole and as component B the compound of formula II.
In a further particular embodiment, the synergistic herbicidal mixture comprises, at least three herbicidal active compounds, a compound of formula I (component A), the compound of formula II (component B) and

    
    
        C) at least one herbicidal compound from the group of the acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, enolpyruvylshikimate 3-phosphate synthase inhibitors (EPSPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporphyrinogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth substances, cell wall biosynthesis inhibitors and a variety of other herbicides.
    
    


For particular preferred embodiments, the respective preferences described above apply analogously.
With a view to the synergistic herbicidal action of the mixtures comprising a component A), B) and C) according to the invention, compounds from amongst groups C1 to C14 or C16, preferably from amongst groups C2, C6 and C12, especially from amongst groups C6 and C12, are preferred as component C).
In particular, compounds from amongst the classes of active ingredients mentioned below are preferred, or the following compounds are very particularly preferred:
C1 acetyl-CoA carboxylase inhibitors (ACC)

    
    
        cyclohexenone oxime ethers, in particular cycloxydim, sethoxydim or tralkoxydim, preferably sethoxydim or tralkoxydim; or
        phenoxyphenoxypropionic esters, in particular clodinafop-propargyl (and, if appropriate, cloquintocet), fenoxaprop-ethyl or fenoxaprop-P-ethyl, preferably clodinafop-propargyl (and, if appropriate, cloquintocet) or fenoxaprop-P-ethyl;
    
    


C2 acetolactate synthase inhibitors (ALS):

    
    
        imidazolinones, in particular imazapyr, imazaquin, imazamethabenz, imazethapyr or imazamoc, preferably imazapyr;
        pyrimidyl ethers, in particular pyrithiobac sodium;
        sulfonamides, in particular florasulam, flumetsulam or metosulam, preferably metosulam; or
        sulfonylureas, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron; especially halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]-carbonyl]-2-(trifluoromethyl)-benzenesulfonamide or sulfosulfuron;
    
    


C3 amides:

    
    
        fluthiamide;
    
    


C4 auxin herbicides:

    
    
        pyridinecarboxylic acids, in particular clopyralid; or
        2,4-D;
    
    


C5 auxin transport inhibitors:

    
    
        diflufenzopyr;
    
    


C6 carotenoid biosynthesis inhibitors:

    
    
        isoxaflutole, mesotrione, isoxachloride, ketospiradox or sulcotrione (chlormesulone), in particular isoxaflutole or sulcotrione;
    
    


C7 enolpyruvylshikimate-3-phosphate synthase inhibitors (EPSPS):

    
    
        glyphosate or sulfosate;
    
    


C8 glutamin synthetase inhibitors:

    
    
        glufosinate-ammonium;
    
    


C9 lipid biosynthesis inhibitors:

    
    
        chloroacetanilides, in particular dimethenamid, S-dimethenamid, acetochlor, metolachlor or S-metolachlor,
        thioureas, in particular benthiocarb;
    
    


C10 mitosis inihibitors:

    
    
        dinitroanilines, in particular pendimethalin;
    
    


C11 protoporphyrinogen IX oxidase inhibitors:

    
    
        diphenyl ethers, in particular acifluorfen or acifluorfen-sodium;
        oxadiazoles, in particular oxadiargyl; or
        cyclic imides, in particular butafenacil, carfentrazone-ethyl, cinidon-ethyl or flumiclorac-pentyl, preferably carfentrazone-ethyl, cinidon-ethyl or flumidorac-pentyl;
        pyrazoles, in particular JV 85;
    
    


C12 photosynthesis inhibitors:

    
    
        pyridate or pyridafol, in particular pyridate;
        benzothiadiazinones, in particular bentazone;
        dipyridylenes, in particular paraquat-dichloride;
        ureas, in particular diuron or isoproturon, preferably diuron;
        phenols, in particular bromoxynil;
        chloridazone;
        triazines, in particular atrazine or terbutylazine; or
        triazinones, in particular metribuzin;
    
    


C13 synergists:

    
    
        oxiranes, in particular tridiphane;
    
    


C14 growth substances:

    
    
        aryloxyalkanoic acids, in particular fluoroxypyr, MCPA or mecoprop-P;
        benzoic acids, in particular dicamba; or
        quinolinecarboxylic acids, in particular quinclorac;
    
    


C16 various other herbicides:

    
    
        triaziflam.
    
    


In particular, compounds from amongst the classes of active ingredients mentioned below are preferred, or the following—compounds are very particularly preferred.
C2 acetolactate synthase inhibitors (ALS):

    
    
        imidazolinones, in particular imazapyr, imazaquin, imazamethabenz, imazethapyr or imazamoc, preferably imazapyr;
        pyrimidyl ethers, in particular pyrithiobac sodium;
        sulfonamides, in particular florasulam, flumetsulam or metosulam, preferably metosulam; or
        sulfonylureas, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron; especially halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfon-amide or sulfo-sulfuron;
    
    


C6 carotenoid biosynthesis inhibitors:

    
    
        isoxaflutole or sulcotrione, preferably isoxaflutole;
    
    


C12 photosynthesis inhibitors:

    
    
        pyridate;
        benzothiadiazinones, in particular bentazone;
        dipyridylenes, in particular paraquat-dichloride;
        ureas, in particular diuron or isoproturon, preferably diuron;
        phenols, in particular bromoxynil;
        chloridazon;
        triazines, in particular atrazine or terbutylazine; or
        triazinones, in particular metribuzin;
    
    


Preferably compounds from amongst the classes C6 and C12 as mentioned above are preferred.
Especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II and as component C a sulfonylurea, in particular iodosulfuron.
Also especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II and as component C isoxaflutole.
Also especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II and as component C pyridate.
Also especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II and as component C a benzothiadiazinones, in particular bentazone.
Also especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II and as component C a triazine, in particular atrazine.
In a further particular embodiment, the synergistic herbicidal mixture comprises, at least two herbicidal active compounds, a compound of formula I (component A), the compound of formula II (component B) and

    
    
        D) a safening effective amount of at least one safener selected from the group of isoxadifen, mefenpyr and fenchlorazol.
    
    


Especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-s-hydroxy-1H-pyrazole, as component B the compound of formula II and as component D isoxadifen.
Also especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II and as component D mefenpyr.
Also especially preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II and as component D fenchlorazol.
In a further particular embodiment, the synergistic herbicidal mixture comprises, at least three herbicidal active compounds, a compound of formula I (component A), the compound of formula II (component B) and

    
    
        C) at least one herbicidal compound from the group of the acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, enolpyruvylshikimate 3-phosphate synthase inhibitors (BPSPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporphyrinogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth substances, cell wall biosynthesis inhibitors and a variety of other herbicides; and
        D) a safening effective amount of at least one safener selected from the group of isoxadifen, mefenpyr and fenchlorazol.
    
    


With a view to the synergistic herbicidal action of the mixtures comprising a component A), B), C) and D) according to the invention, compounds from amongst groups C1 to C14 or C16, preferably from amongst groups C2, C6 and C12, especially from amongst groups C6 and C12, are preferred as component C).
In particular those of the above mentioned mixtures are preferred wherein the safener is isoxadifen.
Also those of the above mentioned mixtures are preferred wherein the safener is mefenpyr.
Also those of the above mentioned mixtures are preferred wherein the safener is fenchlorazol.
Especially those of the above mentioned mixtures are preferred wherein the component C) is selected from amongst the classes of active ingredients mentioned below, or the following compounds:
C2 acetolactate synthase inhibitors (ALS)

    
    
        imidazolinones, in particular imazapyr, imazaquin, imazamethabenz, imazethapyr or imazamoc, preferably imazapyr;
        pyrimidyl ethers, in particular pyrithiobac sodium;
        sulfonamides, in particular florasulam, flumetsulam or metosulam, preferably metosulam; or
        sulfonylureas, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron;
    
    


C6 carotenoid biosynthesis inhibitors:

    
    
        isoxaflutole or sulcotrione, preferably isoxaflutole;
    
    


C12 photosynthesis inhibitors:

    
    
        pyridate;
        benzothiadiazinones, in particular bentazone;
        dipyridylenes, in particular paraquat-dichloride;
        ureas, in particular diuron or isoproturon, preferably diuron;
        phenols, in particular bromoxynil;
        chloridazon;
        triazines, in particular atrazine or terbutylazine; or
        triazinones, in particular metribuzin.
    
    


Extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxa-zol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]-carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodo-sulfuron or sulfosulfuron, and as component D isoxadifen.
In particular extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C iodosulfuron and as component D isoxadifen.
Also extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and as component D mefenpyr.
Also extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and as component D fenchlorazol.
In a further particular embodiment, the synergistic herbicidal mixture comprises, at least four herbicidal active compounds, a compound of formula I (component A), the compound of formula II (component B) and

    
    
        C) at least two herbicidal compound from the group of the acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, enolpyruvylshikimate 3-phosphate synthase inhibitors (EPSPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporphyrinogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth substances, cell wall biosynthesis inhibitors and a variety of other herbicides; and
        D) a safening effective amount of at least one safener selected from the group of isoxadifen, mefenpyr and fenchlorazol.
    
    


With a view to the synergistic herbicidal action of the mixtures comprising a component A), B), C) and D) according to the invention, compounds from amongst groups C1 to C14 or C16, preferably from amongst groups C2, C6 and C12, especially from amongst groups C6 and C12 are preferred as component C).
In particular those of the above mentioned mixtures are preferred wherein the safener is isoxadifen.
Also those of the above mentioned mixtures are preferred wherein the safener is mefenpyr.
Also those of the above mentioned mixtures are preferred wherein the safener is fenchlorazol.
Especially those of the above mentioned mixtures are preferred wherein the two herbicides of the component C) are selected from amongst the classes of active ingredients mentioned below, or the following compounds:
C2 acetolactate synthase inihihitors (ALS):

    
    
        imidazolinones, in particular imazapyr, imazaquin, imazamethabenz, imazethapyr or imazamoc, preferably imazapyr;
        pyrimidyl ethers, in particular pyrithiobac sodium;
        sulfonamides, in particular florasulam, flumetsulam or metosulam, preferably metosulam; or
        sulfonylureas, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron;
    
    


C6 carotenoid biosynthesis inhibitors:

    
    
        isoxaflutole or sulcotrione, preferably isoxaflutole;

C12 photosynthesis inhibitors:

        pyridate;
        benzothiadiazinones, in particular bentazone;
        dipyridylenes, in particular paraquat-dichloride;
        ureas, in particular diuron or isoproturon, preferably diuron;
        phenols, in particular-bromoxynil;
        chloridazon;
        triazines, in particular atrazine or terbutylazine; or
        triazinones, in particular metribuzin.
    
    


Extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and a triazine, in particular atrazine or terbutylazine, and as component D isoxadifen.
In particular extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C iodosulfuron and atrazine, and as component D isoxadifen.
Also in particular extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C iodosulfuron and pyridate, and as component D isoxadifen.
Also extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and a benzothiadiazinone, in particular bentazone, and as component D isoxadifen.
In particular extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C iodosulfuron and bentazone, and as component D isoxadifen.
Extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and a triazine, in particular atrazine or terbutylazine, and as component D mefenpyr.
Also extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and pyridate, and as component D mefenpyr.
Also extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and a benzothiadiazinone, in particular bentazone, and as component D mefenpyr.
Extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and a triazine, in particular atrazine or terbutylazine, and as component D fenchlorazol.
Also extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, is N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and pyridate, and as component D fenchlorazol.
Also extraordinary preferred are synergistic herbicidal mixtures which comprise as component A 4-[2-methyl-3-(4,5-dihydrois-oxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, rimisulfuron; thifensulfuron-methyl, tribenuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]-amino]carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, iodosulfuron or sulfosulfuron, and a benzothiadiazinone, in particular bentazone, and as component D fenchlorazol.
The present invention also extends to herbicidal compositions which comprise a herbicidally active amount of a synergistic herbicidal mixture (comprising components A), B) and, if desired, C) and, if desired, D) as described above), at least one liquid and/or solid carrier and, if desired, at least one surfactant.
The herbicidal compositions and synergistic herbicidal mixtures according to the invention can effect very good control of broad-leaved weeds and grass weeds in crops such as maize, cereals, rice and soya without damaging the crop plants, an effect observed especially even at low rates of application.
Taking into consideration the variety of application method in question, the herbicidal compositions and synergistic herbicidal mixtures according to the invention can additionally be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris ssp. altissima, Beta vulgaris ssp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera und Zea mays. 
Moreover, the herbicidal compositions and synergistic herbicidal mixtures according to the invention can also be used in crops which tolerate the action of herbicides due to breeding, including genetic engineering methods.
The mixtures according to the invention, or the herbicidal compositions comprising them, can be employed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
Suitable inert auxiliaries are mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, such as N-methylpyrrolidone and water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.
Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylaryl sulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl and tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the synergistic herbicidal mixture or the individual active ingredients with a solid carrier.
Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic material, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The concentrations of the mixtures according to the invention in the ready-to-use products can be varied within wide ranges. In general, the formulations comprise from 0.01 to 95% by weight, preferably 0.5 to 90% by weight, of the mixture according to the invention.
The components A) and B) and, if desired, C) and, if desired, D) can be formulated jointly, but also separately, and/or applied to the plants, their environment and/or seeds jointly or separately. It is preferable to apply the active ingredients simultaneously. However, it is also possible to apply them separately.
Moreover, it may be advantageous to apply the herbicidal compositions and synergistic herbicidal mixtures according to the invention, jointly or separately, with additional other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
The mixtures according to the invention and the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spray apparatus, in such a way that they come into as little contact, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil (post-directed, lay-by).
In the case of a post-emergence treatment of the plants, the herbicidal compositions according to the invention are preferably applied by foliar application. Application may be effected, for example, by usual spraying techniques with water as the carrier, using amounts of spray mixture of approx. 100 to 1000 l/ha. The compositions may also be applied by the so-called “low-volume” and “ultra-low-volume” methods, or in the form of so-called granules.
As a rule, the synergistic herbicidal mixtures comprise components A), B) and, if desired, C) and, if desired, D) in such weight ratios that the synergistic effect takes place.
The ratios of component A) and B) in the mixture preferably range from 1:0.001 to 1:500, preferably from 1:0.01 to 1:100, particularly preferably from 1:0.1 to 1:50.
The ratios of components A) and C) in the mixture preferably range from 1:0.002 to 1:800, preferably from 1:0.003 to 1:250, particularly preferably from 1:0.003 to 1:160, especially preferably from 1:0.02 to 1:250, extraordinary preferably from 1:0.02 to 1:160.
The ratios of components A) and D) in the mixture preferably range from 1:0.002 to 1:800, preferably from 1:0.003 to 1:250, particularly preferably from 1:0.02 to 1:160.
The rate of application of pure synergistic herbicidal mixture, i.e. without formulation auxiliaries, amounts to 0.2 to 5000 g/ha, preferably 2 to 2000 g/ha, in particular 8 to 1000 g/ha, of active substance (a.s.), depending on the intended aim, the season, the target plants and growth stage.
The rate of application of 3-heterocyclyl-substituted benzoyl derivative of the formula I is 0.1 to 250 g/ha, as a rule 5 to 250 g/ha, preferably 10 to 150 g/ha, of active substance (a.s.).
The preferred rate of application of the compound of formula II is 0.1 to 250 g/ha, as a rule 1 to 120 g/ha, preferably 10 to 100 g/ha, of active substance (a.s.)
The preferred application rate of the active ingredients of the optional component C are compiled in Table 2.










TABLE 2








Rate of application


Component C
Class of active ingredient
Active ingredient
(g/ha)



















C1
acetyl-CoA carboxylase inhibitors


25-400




cyclohexenone oxime ethers

100-400 





cycloxydim
100-400 





sethoxydim
100-400 





tralkoxydim
100-400 




phenoxyphenoxypropionic esters

25-300





clodinafpop-P-propargyla
25-100





fenoxaprop-ethyl
50-300





fenoxaprop-P-ethyl
25-150


C2
acetolactate synthase inhibitors (ALS)


0.1-800 




imidazolinones

20-800





imazapyr
30-400





imazaquin
50-300





imazamethabenz
100-800 





imazethapyr
30-150





Imazamox
20-120




pyrimidyl ethers

 2-120





pyrithiobac-sodium
 2-120




sulfonamides

 1-225





florasulam
1-20





flumetsulam
25-225





metosulam
1-60




sulfonylureas

0.1-120 





halosulfuron-methyl
 5-120





nicosulfuron
 1-120





primisulfuron-methyl
10-120





prosulfuron
10-120





rimsulfuron
 5-120





thifensulfuron-methyl
10-60 





tribenuron-methyl
10-60 





N-[[[4-methoxy-6-(trifluoromethyl)-
 5-120





1,3,5-triazin-2-yl]amino]carbonyl]-2-





(trifluoromethyl)benzenesulfonamide





iodosulfuron
0.1-10  





sulfosulfuron
10-60 


C3
amides


250-2000




—
fluthiamide
250-2000


C4
auxin herbicides


25-750




pyridinecarboxylic acids

25-750





clopyralid
25-750




—
2,4-D
50-750


C5
auxin transport inhibitors


15-100




—
diflufenzopyr
15-100


C6
carotenoid biosynthesis inhibitors


25-600




—
isoxaflutole
25-200




—
sulcotrione
100-600 




—
mesotrione
25-300




—
isoxachlortole
25-200




—
ketospiradox
25-300


C7
enolpyruvylshikimat-3-phosphate


360-1080



synthase inhibitors (EPSPS)




—
glyphosate
360-1080




—
sulfosate
360-1080


C8
glutamine synthetase inhibitors


10-600




—
glufosinate-ammonium
10-600


C9
lipid biosynthesis inhibitors


 60-4000




chloroacetanilides

 60-4000





dimethenamid
 60-2000





S-dimethenamid
 60-2000





acetochlor
250-4000





metolachlor
 60-4000





S-metolachlor
 60-4000




thioureas

100-4000





benthiocarb
1000-4000 


C10
mitosis inhibitors


375-3000




dinitroanilines

375-3000





pendimethalin
375-3000


C11
protoporphyrinogen IX oxidase


0.5-600 



inhibitors




diphenyl ethers

50-300





acifluorfen
50-300





acifluorfen-sodium
50-300




oxadiazoles

50-600





oxadiargyl
50-600




cyclic imides

0.5-300 





carfentrazone-ethyl
0.5-35  





cinidon-ethyl
3-35





flumiclorac-pentyl
3-35





butafenacil
 5-300





JV 485
50-300


C12
photosynthesis inhibitors


 15-4000




—
pyridate
 30-1500





pyridafol
 30-1000




benzothiadiazinones

 30-1440





bentazone
 30-1440




dipyridylenes

100-800 





paraquat-dichloride
100-800 




ureas

250-1600





diuron
250-1600





isoprotoron
250-1600




phenols

100-700 





bromoxynil
100-700 




chloridazon

500-4000




triazines

 15-4000





atrazine
 15-4000





terbutylazine
250-4000




triazinone

30-300





metribuzin
30-300


C13
synergists


500-1500




oxiranes

500-1500





tridiphane
500-1500


C14
growth substances


 25-1200




aryloxyalkanoic acids

 50-1200





fluoroxypyr
50-400





MCPA
400-1200





mecoprop-P
400-1200




benzoic acids

75-800





dicamba
75-800




quinolinecarboxylic acids

25-600





quinclorac
25-600


C16
various other herbicides
—
triaziflam
50-750





aIf appropriate, 10-50 g/ha cloquintocet may also be added.






The preferred rate of application of the safener D is 0.1 to 500 g/ha. As a rule the application rate for isoxadifen is from 0.5 to 50 g/ha, for mefenpyr from 2 to 100 g/ha and for fenchlorazol from 2 to 100 g/ha.


USE EXAMPLES
The mixtures according to the invention were applied pre- and/or post-emergence (foliar treatment). The herbicidal compounds of component B) and, if desired, of component C) as well as the safener D) were applied in the formulation in which they are present as commercially available product (s).
The herbicidally active compounds of components A), B) and, if desired, C), and, if desired D), were applied in succession or jointly, in the latter case in some cases as a tank mix and in some cases as a readymix, in the form of emulsions, aqueous solutions or suspensions, the vehicle being water (300-400 l/ha). In the case of the field trials, application was effected with the aid of a mobile plot sprayer.
The test period extended over 3 to 8 weeks, and the stands were also observed at later points in time.
Damage by the herbicidal compositions was evaluated with reference to a scale of 0% to 100% in comparison with untreated control plots. 0 means no damage and 100 means complete destruction of the plants.
The following examples will demonstrate, the action of the herbicidal compositions which can be used according to the invention, without excluding the possibility of other uses.
In these examples, the value B at which only an additive effect of the individual active ingredients is to be expected was calculated by the method of S. R. Colby (Calculating synergistic and antagonistic responses of herbicide combinations, Weeds 15, 20 pp (1967)).
This was done using the formula




  E
  =
  
    X
    +
    Y
    -
    
      XY
      100
    
  




where

    X=Percentage of the herbicidal action of component A) at an application rate of a;
    Y=Percentage of the herbicidal action of component B), and, if desired, C), and, if desired, D) at an application rate of b, and, if desired, c, and, if desired, d;
    E=expected herbicidal action of component A)+B), and, if desired C), and; if desired, D) at rates of application a+b, and, if desired, c and, if desired, d (in %).


If the value observed exceeds the value E calculated in accordance with Colby's formula, then synergism is present.
The herbicidal mixtures according to the invention exert a greater herbicidal action than would have been expected according to Colby on the basis of the observed effects of the individual components when used alone.
The results of the tests are shown in Tables 3 to 15 below.
In these studies, the following plants were used:














Scientific name
Common name









Abutilon theophrasti
Velvetleaf



Amaranthus retroflexus
Pigweed



Avena fatua
Wild oat



Bidens pilosa
Hairy beggarticks



Brachiaria plantaginea
Alexandergrass



Commelina benghalensis
Bengal Commelina



Galium aparine
Catchweed



Pharbitis purpurea
Common morningglory



Polygonum persicaria
Ladysthumb

















TABLE 3







Herbicidal action of compound 1a.29 and compound II


(post-emergence treatment; greenhouse)














Avena






Application
fatua

Pharbitis




rate
Damage
Colby
purpurea
Colby



[g/ha ai]
[%]
Value E
Damage [%]
Value E
















Ia.29
3.91
50
—
70
—


Compound II
1.95
50
—
80
—


Ia.29 +
3.91 + 1.95
80
75
98
94


Compound II
















TABLE 4







Herbicidal action of compound 1a.29 and compound II


(post-emergence treatment; greenhouse)














Avena






Application
fatua

Abutilon




rate
Damage
Colby
theophrasti
Colby



[g/ha ai]
[%]
Value E
Damage [%]
Value E
















Ia.29
1.95
25
—
40
—


Compound II
0.98
30
—
30
—


Ia.29 +
1.95 + 0.98
70
48
80
58


Compound II
















TABLE 5







Herbicidal action of compound 1a.29, compound II and atrazine (post-


emergence treatment; field)











Application
Commelina




rate
benghalensis
Colby



[g/ha ai]
Damage [%]
Value E














Ia.29
7.81
40
—


Compound II + Atrazine
3.91 + 62.5
60
—


Ia.29 + Compound
7.81 + 3.91 + 62.5
85
76


II + Atrazine
















TABLE 6







Herbicidal action of compound 1a.29, compound II and


atrazine (post-emergence treatment; greenhouse)













Application
Abutilon

Amaranthus




rate
theophrasti
Colby
retroflexus
Colby



[g/ha ai]
Damage [%]
Value E
Damage [%]
Value E
















Ia.29
3.91
80
—
60
—


Compound II + Atrazine
1.95 + 31.3
50
—
85
—


Ia.29 +
3.91 + 1.95 + 31.3
100
90
98
94


Compound II + Atrazine
















TABLE 7







Herbicidal action of compound 1a.29, compound II and atrazine (post-


emergence treatment; field)











Application
Bidens




rate
pilosa
Colby



[g/ha ai]
Damage [%]
Value E














Ia.29
3.91
30
—


Compound II + Atrazine
1.95 + 31.3
50
—


Ia.29 + Compound
3.91 + 1.95 + 31.3
80
65


II + Atrazine
















TABLE 8







Herbicidal action of compound 1a.29, compound II and


atrazine (post-emergence treatment; greenhouse)













Application
Abutilon

Amaranthus




rate
theophrasti
Colby
retroflexus
Colby



[g/ha ai]
Damage [%]
Value E
Damage [%]
Value E
















Ia.29
1.95
40
—
40
—


Compound II + Atrazine
0.98 + 15.6
25
—
60
—


Ia.29 + Compound
1.95 + 0.98 + 15.6
80
65
85
76


II + Atrazine
















TABLE 9







Herbicidal action of compound 1a.29, compound II and bentazone (post-


emergence treatment; field)











Application
Pharbitis




rate
purpurea
Colby



[g/ha ai]
Damage [%]
Value E














Ia.29
3.91
70
—


Compound II + Bentazone
1.95 + 62.5
60
—


Ia.29 + Compound
3.91 + 1.95 + 62.5
98
88


II + Bentazone
















TABLE 10







Herbicidal action of compound 1a.29, compound II and bentazone


(post-emergence treatment; field)











Application
Polygonum




rate
persicaria
Colby



[g/ha ai]
Damage [%]
Value E














Ia.29
1.95
95
—


Compound II + Bentazone
0.98 + 31.3
70
—


Ia.29 + Compound
1.95 + 0.98 + 31.3
100
99


II + Bentazone
















TABLE 11







Herbicidal action of compound 1a.29, compound II and


bentazone (post-emergence treatment; greenhouse)













Application
Abutilon

Galium




rate
theophrasti
Colby
aparine
Colby



[g/ha ai]
Damage [%]
Value E
Damage [%]
Value E
















Ia.29
7.81
95
—
30
—


Compound II + Bentazone
3.91 + 125
70
—
60
—


Ia.29 + Compound
7.81 + 3.91 + 125
100
99
95
72


II + Bentazone
















TABLE 12







Herbicidal action of compound 1a.29 and X*


(post-emergence treatment; greenhouse)













Application
Abutilon

Bidens




rate
theophrasti
Colby
pilosa
Colby



[g/ha ai]
Damage [%]
Value E
Damage [%]
Value E
















Ia.29
7.81
95
—
60
—


X
3.91
50
—
70
—


Ia.29 + X
7.81 + 3.91
100
98
95
88
















TABLE 13







Herbicidal action of compound 1a.29, X* and atrazine


(post-emergence treatment; field)











Application
Bidens




rate
pilosa
Colby



[g/ha ai]
Damage [%]
Value E














Ia.29
7.81
60
—


X + Atrazine
3.91 + 62.5
80
—


Ia.29 + X + Atrazine
7.81 + 3.91 + 62.5
100
92
















TABLE 14







Herbicidal action of compound 1a.29, X* and atrazine


(post-emergence treatment; greenhouse)













Application
Abutilon

Amaranthus




rate
theophrasti
Colby
retroflexus
Colby



[g/ha ai]
Damage [%]
Value E
Damage [%]
Value E
















Ia.29
3.91
80
—
60
—


X + Atrazine
1.95 + 31.3
40
—
85
—


Ia.29 + X + Atrazine
3.91 + 1.95 + 31.3
95
88
98
94
















TABLE 15







Herbicidal action of compound 1a.29, X* and atrazine


(post-emergence treatment; field)











Application
Brachiaria




rate
plantaginea
Colby



[g/ha ai]
Damage [%]
Value E














Ia.29
3.91
80
—


X + Atrazine
1.95 + 31.3
70
—


Ia.29 + X + Atrazine
3.91 + 1.95 + 31.3
100
94





X* mixture of compound II, iodosulfuron and isoxadifen in a weigh ratio of 30:1:30 (= MaisTer® )

## Claims

1. A synergistic herbicidal mixture comprising
A) 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole or one of its environmentally compatible salts;

and
B) a synergistically effective amount of the compound of formula II





or one of its environmentally compatible salts.

2. A synergistic herbicidal mixture as claimed in claim 1, further comprising component C
C) at least one herbicidal compound from the group consisting of sulfonylurea, bentazone and triazine, wherein said sulfonylurea is selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, triflusulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]-carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, sulfosulfuron or iodosulfuron and said triazine is selected from the group consisting of ametryn, atrazine, cyanazine, desmetryn, dimethamethryn, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbutylazine and trietazine.

3. A synergistic herbicidal mixture as claimed in claim 1 comprising, as component C), a sulfonylurea

4. A synergistic herbicidal mixture as claimed in claim 2 comprising, as component C), a triazine or bentazone

5. A synergistic herbicidal mixture as claimed in claim 2 comprising, as component C), a triazine

6. A synergistic herbicidal mixture as claimed in claim 2, comprising, as component C), atrazine.

7. A synergistic herbicidal mixture as claimed in claim 2, comprising, as component C), bentazone.

8. A synergistic herbicidal mixture as claimed in claim 1, further comprising isoxadifen as component D

9. A synergistic herbicidal mixture as claimed in claim 8, further comprising, as component C,
C) one herbicidal compound from the group consisting of sulfonylurea, bentazone and triazine, wherein said sulfonylurea is selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron-methtyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]-carbonyl]-2-(trifluoromethyl)-benzenesulfonamide, sulfosulfuron or iodosulfuron and said triazine is selected from the group consisting of ametryn, atrazine, cyanazine, desmetryn, dimethamethryn, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbutylazine and trietazine,

10. A synergistic herbicidal mixture as claimed in claim 2, wherein component A) and component C) are present in a weight ratio of 1:0.002 to 1:800.

11. A synergistic herbicidal mixture as claimed in claim 8, wherein component A) and component D) are present in a weight ratio of 1:0.002 to 1:800.

12. A synergistic herbicidal mixture comprising
A) 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole or one of its environmentally compatible salts;
or one of its environmentally compatible salts;

and
B) a synergistically effective amount of the compound of formula II





or one of its environmentally compatible salts;
C) at least one herbicidal compound from the group consisting of sulfonylurea, bentazone and triazine, wherein said sulfonylurea is selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]-carbonyl]-2-(trifluoromethyl )-benzenesulfonamide, sulfosulfuron or iodosulfuron and said triazine is selected from the group consisting of ametryn, atrazine, cyanazine, desmetryn, dimethamethryn, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbutylazine and trietazine

and
D) a safening effective amount of isoxadifen;

or an environmentally compatible salt or ester thereof.

13. A herbicidal composition comprising a herbicidally active amount of a synergistic herbicidal mixture of claim 12, and at least one inert liquid and/or solid carrier therefor.

14. A process for preparing a herbicidal composition of claim 13, comprising mixing together component A) component B) if desired, component C) if desired, component D), and at least one inert liquid and/or solid carrier therefor.

15. A method of controlling undesired vegetation, comprising applying simultaneously or separately to said vegetation, the environment of said vegetation and/or seeds of said vegetation
A) 4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole. or one of its environmentally compatible salts; and
B) a synergistically effective amount of the compound of formula II





or one of its environmentally compatible salts.

16. The method of claim 15, wherein leaves of the undesired vegetation are treated.

17. The composition of claim 13, wherein the composition further comprises at least one surfactant.

18. The method according to claim 15, further comprising components
C) at least one herbicidal compound from the group consisting of sulfonylurea, bentazone and triazine, wherein said sulfonylurea is selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]-carbonyl]-2-(trifluoromethyl) -benzenesulfonamide, sulfosulfuron or iodosulfuron and said triazine is selected from the group consisting of ametryn, atrazine, cyanazine, desmetryn, dimethamethryn, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbutylazine and trietazine; and
D) a safening effective amount of isoxadifen or an environmentally compatible salt or ester thereof.

19. The method of claim 18, wherein at least two of component A), component B), component C), and component D are applied in the form of a mixture.

20. The method of claim 18, wherein the components A), B), C) and D) are applied separately.