WO2004004463A1 - Synergistically acting herbicidal mixtures - Google Patents

Synergistically acting herbicidal mixtures Download PDF

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Publication number
WO2004004463A1
WO2004004463A1 PCT/EP2003/007321 EP0307321W WO2004004463A1 WO 2004004463 A1 WO2004004463 A1 WO 2004004463A1 EP 0307321 W EP0307321 W EP 0307321W WO 2004004463 A1 WO2004004463 A1 WO 2004004463A1
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WIPO (PCT)
Prior art keywords
component
methyl
inhibitors
compound
formula
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PCT/EP2003/007321
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French (fr)
Inventor
William B. O'neal
Elmar Kibler
Matthias Witschel
Herve R. Vantieghem
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Basf Aktiengesellschaft
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Priority to YUP-1154/04A priority Critical patent/RS50941B/en
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EA200500136A priority patent/EA007386B1/en
Priority to MXPA05000049A priority patent/MXPA05000049A/en
Priority to EP03740437A priority patent/EP1521529B1/en
Priority to DE60312864T priority patent/DE60312864T2/en
Priority to AU2003281252A priority patent/AU2003281252A1/en
Priority to US10/519,978 priority patent/US7632782B2/en
Priority to CA2490499A priority patent/CA2490499C/en
Priority to JP2004518742A priority patent/JP4739752B2/en
Priority to BR0312497-5A priority patent/BR0312497A/en
Priority to UAA200500947A priority patent/UA81633C2/en
Publication of WO2004004463A1 publication Critical patent/WO2004004463A1/en
Priority to HRP20050129AA priority patent/HRP20050129B1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • the present invention relates to a synergistic herbicidal mixture comprising
  • R 1 , R 3 "' are halogen, C x -C 6 -alkyl, C x -C 6 -haloalkyl, C x -C 6 - alkoxy, C x -C 3 -haloalkoxy, C x -C 6 -alkylthio, C x -C 6 - alkylsulfinyl or C x - C e - lkylsulfonyl;
  • R 2 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, C x -C 4 -alkyl, C x -C 4 - alkoxy, C 1 -C 4 -haloalkyl, C x -C 4 -haloalkoxy or C x -C 4 - alkylthio;
  • R 4 is hydrogen, halogen or C x -C 3 -alkyl ;
  • R 5 is C x - C ⁇ -alkyl
  • R 6 is hydrogen or C x -C 6 -alkyl
  • ACC acetyl-CoA carboxylase inhibitors
  • ALS acetolactate synthase inhibitors
  • 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 othe "herbicides;
  • ACC acetyl-CoA carboxylase inhibitors
  • ALS acetolactate synthase inhibitors
  • amides auxin herbicides
  • auxin transport inhibitors carotenoid biosynthesis inhibitors
  • EPSPS enolpyruvylshikimate 3-phosphate synthase inhibitors
  • glutamine synthetase inhibitors
  • 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.
  • 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.
  • ACC acetyl-CoA carboxylase inhibitors
  • 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 protoporphyrino- gen 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.
  • suitable growth substances are aryloxyalkanoic acids, benzoic acids or quinolinecarboxylic acids .
  • 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.
  • 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.
  • EPSPS enolpyruvylshikimate 3-phosphate synthase inhibitors
  • 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:
  • CI acetyl-CoA carboxylase inhibitors for example - cyclohexenone oxime ethers, such as alloxydim, . . . ⁇ lethodim, 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,
  • C2 acetolactate synthase inhibitors 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, KIH-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
  • C3 amides for example allidochlor (CDAA) , benzoylprop-ethyl, bromobutide, chlorthiamid, diphenamid, etobenzanid (benzchlomet) , fluthiamide, fosa in or monalide;
  • CDAA allidochlor
  • benzoylprop-ethyl bromobutide
  • chlorthiamid diphenamid
  • etobenzanid benzchlomet
  • fluthiamide fosa in or monalide
  • C4 auxin herbicides for example pyridinecarboxylic acids, such as clopyralid or picloram; or
  • C5 auxin transport inhibitors for example naptalame or diflufenzopyr
  • C6 carotenoid biosynthesis inhibitors for example benzofenap, clomazone (dimethazone) , diflufenican, luorochlo idone, fluridone, pyrazolynate, pyrazoxyfen, isoxaflutole, isoxachlortole, mesotrione, sulcotrione (chlormesulone) , ketospiradox, flurtamone, norflurazon or amitrol; C7 enolpyruvylshikimate-3 -phosphate synthase inhibitors ( ⁇ PSPS) , for example glyphosate or sulfosate;
  • ⁇ PSPS enolpyruvylshikimate-3 -phosphate synthase inhibitors
  • 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-dimethen- amid, 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, prpsulfocarb, thiobencarb (benthiocarb) , tri-allate or vernolate ; or benfuresate or perfluidone;
  • anilides such as anilofos or me
  • CIO 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;
  • carbamates such as asulam, carbetamid, chlorpropham, orbencarb, pronamid (propyzamid) , propham or tiocarbazil
  • - dinitroanilines such as benefin, butralin, dinitramin, ethalfluralin, fluchloralin, oryzalin,
  • Cll 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 -
  • 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 paraquat-dichloride; ureas, such as chlorbromuron, chlorotoluron, difenoxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, me,thabenzthiazuron, methazole, metobenzuron, metoxuron, m ⁇ olinuron, neburon, siduron or tebuthiuron; phenols, such as
  • 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;
  • 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
  • quinolinecarboxylic acids such as quinclorac or quinmerac
  • C15 cell wall synthesis inhibitors for example iso
  • C16 various other herbicides, for example - dichloropropionic acids , such as dalapon; dihydrobenzof urans , 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, dy ron, eglinazin-ethyl , endothall, ethiozin, flucabazone, f luorbentranil, flupoxam, isocarbamid, isopropalin, karbutilate,
  • the compound of formula II (common name foramsulfuron) is disclosed in US 5,922,646.
  • herbicidally active compounds from amongst groups CI to C16 are described, for example, in
  • 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, “KIH- 6127” p. 47, “prosulfuron” p. 53, “KIH-2023” p. 61, “metobenzuron” p. 67) .
  • 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 3-heterocyclyl-substituted benzoyl derivatives of the formula I can exist, or be used, in the form of the pure enantiomers and . also as ra ⁇ emates 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 CI to C16 and/or the safeners- may also -exist in the-form of thei -env ronmentally 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 C x -C 4 -alkyl, hydroxy-C x -C 4 - alkyl, C x -C 4 -alkoxy-C x -C 4 -alkyl, hydroxy-C x -C 4 -alkoxy-C x -C 4 -alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-l-oxy) eth-l-yl ammonium, di (2-hydroxy
  • 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 C x -C 4 -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 C x -C x0 - alkylesters,' for example methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, pentyl-, mexyl- (1-ethyl-hexyl-) or isooctyl- (2-ethylhexyl-) esters, C x -C 4 -alkoxyethylesters, for example methoxyethyl-, ethoxyethyl- or butoxyethylesters, allylesters, propargylesters and oxetan-3-ylesters.
  • R 1 halogen such as chlorine or bromine, C x -C 6 -alkyl such as methyl or ethyl or C x -C 6 -alkylsulfonyl such as methylsulfonyl or ethylsulfonyl; especially preferably chlorine, methyl or methylsulfonyl;
  • R 2 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, C x -C 4 -alkyl, C x -C 4 - alkoxy, C x -C 4 -haloalkyl, C x -C 4 -haloalkoxy or C x -C 4 - lkylthio; especially preferably isoxazol-5-yl, 3-methyl-isoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 5-methyl-4, 5-dihydroisoxazol-yl, 5- ethyl-4, 5-dihydroisoxazol-3-yl or 4,5-dimethyl-4,5- dihydroisox
  • halogen such as chlorine or bromine or C x -C 6 -alkylsulfonyl such as methylsulfonyl or ethylsulfonyl; especially preferably chlorine, methylsulfonyl or ethyl- sulfonyl;
  • R 4 hydrogen or methyl; especially preferably hydrogen
  • R 5 is C x -C 6 -alkyl , such as methyl , ethyl, propyl, 1-methylethyl , butyl ⁇ i-methylpropyl or 2-methylpropyl ; especially preferably methyl , ethyl or 1-methylethyl ;
  • R s hydrogen or C x -C 6 -alkyl, such as methyl or ethyl ; especially preferably hydrogen or methyl .
  • the compounds lb in particular the compounds lb.l to lb.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the sodium salt:
  • the compounds Ic in particular the compounds Ic.l to Ic.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the lithium salt:
  • the compounds Id in particular the compounds Id.l to Id.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the potassium salt:
  • the compounds Ie in particular the compounds le.l to Ie.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the ammonium salt :
  • R is hydrogen
  • halogen C x - C 4 -alkyl, C x -C 4 -alkoxy, C x -C 4 -haloalkyl, C x -C 4 -haloalkoxy or C x -C 4 -alkylthio.
  • the 3- heterocyclyl-substituted benzoyl derivatives of the formula I where
  • R 2 is isoxazol-3-yl which can be unsubstituted or mono- or polysubstituted by halogen, C x -C 4 -alkyl, C x -C 4 -alkoxy, C x - C 4 -haloalkyl, C x -C 4 -haloalkoxy or C x -C 4 -alkylthio;
  • R 4 is hydrogen
  • R 2 is isoxazol-5-yl, which can be unsubstituted or mono- or polysubstituted by halogen, C x -C 4 -alkyl, C x -C 4 -alkoxy, C x - C ⁇ haloalkyl, C x -C 4 -haloalkoxy or C x -C 4 -alkylthio;
  • R 4 is hydrogen
  • R 2 is a heterocyclic radical selected from the group:
  • R 2 is 4,5-dihydroisoxazol-3-yl which can be unsubstituted or mono- or polysubstituted by halogen, C x -C 4 -alkyl, C x - C 4 -alkoxy, C x -C 4 -haloalkyl, C x -C 4 -haloalkoxy or C x -C 4 - alkylthio;
  • R 4 is hydrogen
  • R x is halogen or C x -C 6 -alkyl
  • R 2 is-.4,5-dihydroisoxazol-3-yl which can be unsubstituted or mono- or polysubstituted by halogen, C x -C 4 -alkyl, C x - C 4 - lkoxy, C x -C 4 -haloalkyl, C x -C 4 -haloalkoxy or C x -C 4 - alkylthio;
  • R 3 is C x -C 3 -alkylsulfonyl
  • R 4 is hydrogen
  • the synergistic herbicidal mixture comprises, two herbicidal active compounds, a compound of formula I (component A) and the compound of formula II (component B) .
  • a compound of formula I component A
  • the compound of formula II component B
  • the respective preferences described above apply analogously.
  • the synergistic herbicidal mixture comprises as component A 4- [2-methyl-3- (4 , 5-dihydroisoxazol-3-yl) -4- methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-lH-pyrazole and as component B the compound of formula II.
  • 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
  • ACC acetyl-CoA carboxylase inhibitors
  • ALS acetolactate synthase inhibitors
  • amides auxin herbicides
  • auxin transport inhibitors carotenoid biosynthesis inhibitors
  • EPSPS enolpyruvylshikimate 3-phosphate synthase
  • CI 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 imidazolinones, in particular imazapyr, imazaquin, imazamethabenz, imazethapyr or imazamoc, preferably imazapyr; - pyrimidyl ethers, in particular pyrithiobac sodium; sulfonamides, in particular florasulam, flumetsulam r 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) - benzenesulf
  • 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;
  • EPSPS enolpyruvylshikimate-3 -phosphate synthase inhibitors
  • 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;
  • CIO mitosis inhibitors dinitroanilines, in particular pendimethalin;
  • Cll 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 V 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;
  • C2 acetolactate synthase inhibitors imidazolinones, in particular imazapyr, imazaquin, imazamethabenz, imazethapyr or imazamoc, preferably lmazapyi ; 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) - benzene
  • C6 carotenoid biosynthesis inhibitors - isoxa lutole or sulcotrione, preferably isoxa lutole;
  • 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;
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- H-p'yrazole, as component B the compound of formula II and as component C a sulfonylurea, in particular iodosulfuron.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-lH-pyrazole, as component B the compound of formula II and as component C isoxaflutole .
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-pyrazole, as component B the compound of formula II and as component C pyridate.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-pyrazole, as component B the compound of formula II and as component C a benzothiadiazinones, in particular bentazone.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-pyrazole, as component B the compound of formula II and as component C a triazine, in particular atrazine.
  • 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
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- lH-pyrazole, as cbmptinenf B the compound of formula TI " and as' component D isoxadifen.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-pyrazole, as component B the compound of formula II and as component D mefenpyr.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-pyrazole, as component B the compound of formula II and as component D fenchlorazol .
  • 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
  • ACC acetyl-CoA carboxylase inhibitors
  • ALS acetolactate synthase inhibitors
  • amides auxin herbicides
  • auxin transport inhibitors carotenoid biosynthesis inhibitors
  • EPSPS enolpyruvylshikimate 3-phosphate
  • the safener is f nchlorazol .
  • the component C) is selected from amongst the classes of active ingredients mentioned below, or the following compounds:
  • C2 acetolactate synthase inhibitors 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,
  • C6 carotenoid biosynthesis inhibitors isoxaflutole or sulcotrione, preferably isoxaflutole;
  • - ' benz thiadiazinones 'in-particular -bentazoae; 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.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydro- isoxa-zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- lH-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) -l,3,5-triazin-2-yl] -amino] - carbonyl] -2- (trifluoromethyl) -benzenesulfonamide, iodo- sulfuron or sulfosulfuron, and as component D isoxadifen
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1- methyl-5-hydroxy-IH-pyrazole, as component B the compound of formula II, as component C iodosulfuron and as component D isoxadifen.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosul- furon-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 1 synergistic'"herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-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.
  • 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
  • ACC acetyl-CoA carboxylase inhibitors
  • ALS acetolactate synthase inhibitors
  • amides auxin herbicides
  • auxin transport inhibitors carotenoid biosynthesis inhibitors
  • EPSPS enolpyruvylshikimate 3-phosphate synthase inhibitors
  • 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 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
  • C12 photosynthesis inhibitors pyridate; benzothiadiazinones, in particular bentazone; dipyridylenes, in particular paraquat-dichloride; ureas, in particular diuron or isoproturon, preferably diuron; phenols,.- in particular -brotnoxynil; chloridazon; triazines, in particular atrazine or terbutylazine; or - triazinones, in particular metribuzin.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- IH-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 terbutyla
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1- methyl-5-hydroxy-IH-pyrazole, as component B the compound of formula II, as component C iodosulfuron and atrazine, and as component D isoxadifen.
  • synergistic herbicidal mixtures which comprise as component A 4- [2- methyl-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonyl- benzoyl] -l-methyl-5-hydroxy-IH-pyrazole, as component B the compound of formula II, as component C iodosulfuron and pyridate, and as component D isoxadifen.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosul- furon, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N- [ “ [ [4-me “ thoxy"-6- ' trifiuo bmetnyl) -1, 3 , 5-triazin-2-yl] - amino] carbonyl] -2- (trifluoromethyl) -benzenesulfonamide, iodosulfuron or sulfosulfuron, and a benzothi
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1- methyl-5-hydroxy-IH-pyrazole, as component B the compound of formula II, as component C iodosulfuron and bentazone, and as component D isoxadifen.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- IH-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 terbuty
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-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.
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hyd oxy-IH-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) -l,3,5-triazin-2-yl] - amino] carbonyl] -2- (trifluoromethyl) -benzenesulfonamide, iodosulfuron or sulfosulfuron, and a benzo
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- IH-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 terbuty
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-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 fenchlorazol .
  • synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5- dihydrois-oxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosul- furon-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
  • 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.
  • a synergistic herbicidal mixture comprising components A) , B) and, if desired, C) and, if desired, D) as described above
  • 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.
  • 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.
  • 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.
  • Ricin ⁇ s communis Saccharum officihairum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera und Zea mays.
  • 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.
  • 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.
  • 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.
  • 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 derivative
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • 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.
  • 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 isoo
  • 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.
  • concentrations of the mixtures according to the invention in the ready-to-use products can be varied within wide ranges.
  • the' formulation's 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.
  • herbicidal compositions and synergistic herbicidal mixtures according to the invention 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.
  • additional other crop protection agents for example with pesticides or agents for controlling phytopathogenic fungi or bacteria.
  • 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) .
  • 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 1/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 .
  • the synergistic herbicidal mixtures comprise comporieh 'AJ , 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.)
  • 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.
  • 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.
  • 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).
  • 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 ⁇ a's a readymix, in the form of emulsions, aqueous solutions or suspensions, the vehicle being water (300 - 400 1/ha) .
  • application was effected with the aid of a mobile plot sprayer.
  • 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 value E 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) ) .
  • 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 %) .
  • 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.
  • Table 3 Herbicidal action of compound la.29 and compound II (post-emergence treatment; greenhouse)
  • Table 7 Herbicidal action of compound la.29, compound II and atrazine (post-emergence treatment; field)
  • Table 8 Herbicidal action of compound la.29, compound II and atrazine (post-emergence treatment; greenhouse)
  • Table 10 Herbicidal action of compound la.29, compound II and bentazone (post-emergence treatment; field)
  • Table 11 Herbicidal action of compound la.29, compound II and bentazone (post-emergence treatment; greenhouse)
  • Table 12 Herbicidal action of compound la.29 and X* (post-emergence treatment; greenhouse)
  • Table 13 Herbicidal action of compound la.29, X* and atrazine (post -emergence treatment; field)
  • Table 14 Herbicidal action of compound la.29, X* and atrazine (post -emergence treatment; greenhouse)
  • Table 15 Herbicidal action of compound la.29, X* and atrazine (post-emergence treatment; field)

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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 alkylsulfony; 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 desire, D) at least a safener. Compositions comprising these mixtures, processes for the preparation of these compositions, and their use for controlling undesired plants.

Description

Synergistically acting herbicidal mixtures
The present invention relates to a synergistic herbicidal mixture comprising
A) at least one 3-heterocyclyl-substituted benzoyl derivative of the formula I
Figure imgf000002_0001
in which the variables have the following meanings:
R1, R3 "' are halogen, Cx-C6-alkyl, Cx-C6-haloalkyl, Cx-C6- alkoxy, Cx-C3-haloalkoxy, Cx-C6-alkylthio, Cx-C6- alkylsulfinyl or Cx - Ce - lkylsulfonyl;
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, Cx-C4-alkyl, Cx-C4- alkoxy, C1-C4-haloalkyl, Cx-C4-haloalkoxy or Cx-C4- alkylthio;
R4 is hydrogen, halogen or Cx-C3 -alkyl ;
R5 is Cx - Cβ -alkyl ;
R6 is hydrogen or Cx-C6-alkyl;
or one of its environmentally compatible salts;
and B) a synergistically effective amount of the compound of formula II
Figure imgf000003_0001
or one of its environmentally compatible salts;
and, if desired,
C) at lea "Vst 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 othe "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 protoporphyrino- gen 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:
CI acetyl-CoA carboxylase inhibitors (ACC) , for example - cyclohexenone oxime ethers, such as alloxydim, . . . σlethodim, 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, KIH-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, tribenuro -methyl, triflusulfuron-methyl,
N- [ [ [4-methoxy-6- (trifluoromethyl) -1, 3 , 5-triazin-2- ylj amino] carbonyl] -2- (trifluoro-methyl) -benzenesulfon- amide, sulfosulfuron or iodosulfuron;
C3 amides, for example allidochlor (CDAA) , benzoylprop-ethyl, bromobutide, chlorthiamid, diphenamid, etobenzanid (benzchlomet) , fluthiamide, fosa in 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, luorochlo idone, fluridone, pyrazolynate, pyrazoxyfen, isoxaflutole, isoxachlortole, mesotrione, sulcotrione (chlormesulone) , ketospiradox, flurtamone, norflurazon or amitrol; C7 enolpyruvylshikimate-3 -phosphate synthase inhibitors (ΞPSPS) , 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-dimethen- amid, 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, prpsulfocarb, thiobencarb (benthiocarb) , tri-allate or vernolate ; or benfuresate or perfluidone;
CIO 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;
Cll 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 paraquat-dichloride; ureas, such as chlorbromuron, chlorotoluron, difenoxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, me,thabenzthiazuron, methazole, metobenzuron, metoxuron, mόήolinuron, neburon, siduron or tebuthiuron; phenols, such as bromoxynil or ioxynil; - chloridazon; triazines, such as ametryn, atrazine, cyanazine, desmetryn, dimet amethryn, hexazinone, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbutylazine or trietazine; - triazinones, such as metamitron or metribuzin; r. ..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; dihydrobenzof urans , 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, dy ron, eglinazin-ethyl , endothall, ethiozin, flucabazone, f luorbentranil, flupoxam, isocarbamid, isopropalin, karbutilate, mefluidide, monuron, napropamide , napropanilide, nitralin, oxaciclomef one , phenisopham, piperophos , procyazine, profluralin, pyributicarb, secbumeton, suifallate (CDEC) , terbucarb, triaziflam, triazofenamid or t imeturon;
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 US 5,922,646.
The herbicidally active compounds from amongst groups CI 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, "ethamet- sulfuron-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, "etobenza id (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, "dichlprprop-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, "flu etsulam" p. 227, "amidosulfuron" p. 151, "halosulfuron-methyl" p. 148,
"rimsulfuron" p. 138, "tribenuron-methyl" p. 139, "triflusul- furon-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, "i azapic" 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, "vernoiate" 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, "prof.luralin" ~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, "ioxynil" 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, "chloridazon" 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, "butami-fos"— ,.2-28r.."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, "KIH- 6127" p. 47, "prosulfuron" p. 53, "KIH-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',1)' 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 raσemates 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 CI to C16 and/or the safeners- may also -exist in the-form of thei -env ronmentally 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 Cx-C4-alkyl, hydroxy-Cx-C4- alkyl, Cx-C4-alkoxy-Cx-C4-alkyl, hydroxy-Cx-C4-alkoxy-Cx-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-l-oxy) eth-l-yl ammonium, di (2-hydroxyeth-l- yl) ammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri (Cx-C4-alkyl) sulfonium and sulfoxonium ions, preferably, tri (Cx-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 Cx-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 Cx-Cx0- alkylesters,' for example methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, pentyl-, mexyl- (1-ethyl-hexyl-) or isooctyl- (2-ethylhexyl-) esters, Cx-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- erbioidal 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, Cx-C6-alkyl such as methyl or ethyl or Cx-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, Cx-C4-alkyl, Cx-C4- alkoxy, Cx-C4-haloalkyl, Cx-C4-haloalkoxy or Cx-C4- lkylthio; especially preferably isoxazol-5-yl, 3-methyl-isoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 5-methyl-4, 5-dihydroisoxazol-yl, 5- ethyl-4, 5-dihydroisoxazol-3-yl or 4,5-dimethyl-4,5- dihydroisoxazol-3-yl;
halogen such as chlorine or bromine or Cx-C6-alkylsulfonyl such as methylsulfonyl or ethylsulfonyl; especially preferably chlorine, methylsulfonyl or ethyl- sulfonyl;
R4 hydrogen or methyl; especially preferably hydrogen;
R5 is Cx-C6-alkyl , such as methyl , ethyl, propyl, 1-methylethyl , butyl ^ i-methylpropyl or 2-methylpropyl ; especially preferably methyl , ethyl or 1-methylethyl ;
Rs hydrogen or Cx-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 la, in particular the compounds la.l to la.47, which are mentioned in Table 1 which follows:-"""" " "" -• — - * «• ...»-...,...- .
Table 1
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000016_0001
Figure imgf000017_0003
Also very particularly preferred are the compounds lb, in particular the compounds lb.l to lb.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the sodium salt:
Figure imgf000017_0001
Also very particularly preferred are the compounds Ic, in particular the compounds Ic.l to Ic.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the lithium salt:
Figure imgf000017_0002
Also very particularly preferred are the compounds Id, in particular the compounds Id.l to Id.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the potassium salt:
Figure imgf000018_0001
Also very particularly preferred are the compounds Ie, in particular the compounds le.l to Ie.47, which differ from the compounds la.l to Ia.47 only by the fact that they are present as the ammonium salt :
Figure imgf000018_0002
Very particularly preferred are, especially, the compounds la, especially the compounds la.l to Ia.47.
Very particularly preferred are, moreover, the 3- heterocyclyl-substituted benzoyl derivatives of the formula I, where
R is hydrogen.
Very particularly preferred are, moreover, the 3-heterocyclyl substituted benzoyl derivatives of the formula I where
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, Cx- C4-alkyl, Cx-C4-alkoxy, Cx-C4-haloalkyl, Cx-C4-haloalkoxy or Cx-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, Cx-C4-alkyl, Cx-C4-alkoxy, Cx- C4-haloalkyl, Cx-C4-haloalkoxy or Cx-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, Cx-C4-alkyl, Cx-C4-alkoxy, Cx- C^haloalkyl, Cx-C4-haloalkoxy or Cx-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- lH-pyrazole .
Most particularly preferred is also 4- [2-methyl-3- (3-methyl- isoxazol-5-yl) -4"-ώethylsulfoxyl-benzoyl] -1-methyl-5- ydroxy- lH-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, Cx-C4-alkyl, Cx-C4-alkoxy, Cx- C4-haloalkyl, Cx-C4-haloalkoxy or Cx-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, Cx-C4-alkyl, Cx- C4-alkoxy, Cx-C4-haloalkyl, Cx-C4-haloalkoxy or Cx-C4- alkylthio;
R4 is hydrogen.
Most particularly preferred are the 3-heterocyclyl- substituted benzoyl derivatives of the formula I where
Rx is halogen or Cx-C6-alkyl; and
R2 is-.4,5-dihydroisoxazol-3-yl which can be unsubstituted or mono- or polysubstituted by halogen, Cx-C4-alkyl, Cx- C4- lkoxy, Cx-C4-haloalkyl, Cx-C4-haloalkoxy or Cx-C4- alkylthio;
R3 is Cx-C3-alkylsulfonyl;
R4 is hydrogen.
Most especially preferred s -4~[2~chloro-3- (4 , 5-dihydro- isoxazol-3-yl) -4-methylsulfonylbenzoyl] -1-methyl-5-hydroxy- lH-pyrazole .
Most particularly preferred is also 4- [2-methyl-3- (4,5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-lH-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] -l-methyl-5-hydroxy-lH-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 :paxti uletr 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 CI 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: CI 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 r 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, primi- sulfuron-methyl, prosulfuron, rimsulfuron, thifen-
'"■ ■" ^sύlfuron-methyi, 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;
CIO mitosis inhibitors: dinitroanilines, in particular pendimethalin;
Cll 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 V 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 : -ϊ'5, 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 lmazapyi ; 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: - isoxa lutole or sulcotrione, preferably isoxa lutole;
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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- H-p'yrazole, 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] -l-methyl-5- hydroxy-lH-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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- lH-pyrazole, as cbmptinenf B the compound of formula TI" and as' component D isoxadifen.
Also especially preferred are synergistic herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4,5-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- lH-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 (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 he'ybicides; 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 CI 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 f nchlorazol . 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;
- ' benz thiadiazinones, 'in-particular -bentazoae; 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-dihydro- isoxa-zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- lH-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) -l,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-IH-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] -l-methyl-5- hydroxy-IH-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosul- furon-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" are1 synergistic'"herbicidal mixtures which comprise as component A 4- [2-methyl-3- (4, 5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-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 CI 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 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 -brotnoxynil; 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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy- IH-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-IH-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] -l-methyl-5-hydroxy-IH-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] -l-methyl-5- hydroxy-IH-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosulfuron-methyl, nicosulfuron, primisulfuron-methyl, prosul- furon, rimsulfuron, thifensulfuron-methyl, tribenuron-methyl, N- ["[ [4-me"thoxy"-6-' trifiuo bmetnyl) -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-IH-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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- IH-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] -l-methyl-5- hydroxy-IH-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] -l-methyl-5- hyd oxy-IH-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) -l,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-dihydro- isoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy- IH-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] -l-methyl-5- hydroxy-IH-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 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] -l-methyl-5- hydroxy-IH-pyrazole, as component B the compound of formula II, as component C a sulfonylurea, in particular halosul- furon-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 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'j 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 tabaσum (N.rustica) , Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre,
Ricinύs communis, Saccharum officihairum, 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' formulation's" 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 1/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 comporieh 'AJ , 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
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
If 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^a's a readymix, in the form of emulsions, aqueous solutions or suspensions, the vehicle being water (300 - 400 1/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 E 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 XY
E = X + Y -
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:
Figure imgf000046_0001
Table 3: Herbicidal action of compound la.29 and compound II (post-emergence treatment; greenhouse)
Figure imgf000047_0001
Table 4: Herbicidal action of compound la.29 and compound II (post-emergence treatment; greenhouse)
Figure imgf000047_0002
Table 5: Herbicidal action of compound la.29, compound II and atrazine (post-emergence treatment; field)
Figure imgf000048_0001
Table 6: Herbicidal action of compound la.29, compound II and atrazine (pos -emergence treatment; greenhouse)
Figure imgf000048_0002
Table 7: Herbicidal action of compound la.29, compound II and atrazine (post-emergence treatment; field)
Figure imgf000049_0001
Table 8: Herbicidal action of compound la.29, compound II and atrazine (post-emergence treatment; greenhouse)
Figure imgf000049_0002
Table 9: Herbicidal action of compound la.29, compound II and bentazone (post-emergence treatment; field)
Figure imgf000050_0001
Table 10: Herbicidal action of compound la.29, compound II and bentazone (post-emergence treatment; field)
Figure imgf000050_0002
Table 11: Herbicidal action of compound la.29, compound II and bentazone (post-emergence treatment; greenhouse)
Figure imgf000051_0001
Table 12: Herbicidal action of compound la.29 and X* (post-emergence treatment; greenhouse)
Figure imgf000051_0002
Table 13: Herbicidal action of compound la.29, X* and atrazine (post -emergence treatment; field)
Figure imgf000052_0001
Table 14: Herbicidal action of compound la.29, X* and atrazine (post -emergence treatment; greenhouse)
Figure imgf000052_0002
Table 15: Herbicidal action of compound la.29, X* and atrazine (post-emergence treatment; field)
Figure imgf000053_0001
X* mixture of compound II, iodosulfuron and isoxadifen in a weigh ratio of 30:1:30 (= MaisTer*)

Claims

We claim :
1. A synergistic herbicidal mixture comprising
A) at least one 3-heterocyclyl-substituted benzoyl derivative of the formula I
Figure imgf000054_0001
in which the variables have the following meanings:
Figure imgf000054_0002
alkoxy, Cj-Cg-haloalkoxy,
Figure imgf000054_0003
alkylsulfinyl or Ci-Cg-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, Cx-C4-alkyl, C1-C4- alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or Cα-C4- alkylthio;
R* is hydrogen, halogen or Cx-C6-alkyl;
R5 is Ci-Cg-alkyl;
Rs is hydrogen or C, -C6-alkyl;
or one of its environmentally compatible salts;
and B) a synergistically effective amount of the compound of formula II
Figure imgf000055_0001
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 or 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.
A synergistic herbicidal mixture as claimed in claims 1, comprising, as component A) , a 3-heterocyclyl-substituted benzoyl derivative of the formula I, where R4 is hydrogen.
3. A synergistic herbicidal mixture as claimed in any of claims 1 to 2, comprising, as component A), a 3-heterocyclyl- substituted benzoyl derivative of the formula I, where
R1 is halogen, C,.-C6-alkyl or Cx-C6-alkylsulfonyl;
R3 is halogen or
Figure imgf000056_0001
.
4. A synergistic herbicidal mixture as claimed in any of claims 1 to 3, comprising, as component A), a 3-heterocyclyl- substituted benzoyl derivative of the formula I, where
R2 is 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, C^Q,-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, Cx-C4-haloalkoxy or CX-Q. -alkylthio.
5. A synergistic herbicidal mixture as claimed in any of claims . 1 to 4, comprising, as component A) , a 3-heterocyclyl- substituted benzoyl derivative of the formula I, where
R2 is isoxazol-5-yl, 3-methyl-isoxazol-5-yl, 4,5- dihydroisoxazol-3-yl, 5-methyl-4, 5-dihydroisoxazol-3-yl,
5-ethyl-4,5-dihydroisoxazol-3-yl or 4, 5-dimethyl-4,5- dihydroisoxazol-3-yl .
6. A synergistic herbicidal mixture as claimed in any of claims 1 to 5, comprising, as component A), 4- [2-chloro-3- (4,5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-pyrazole .
7. A synergistic herbicidal mixture as claimed in any of claims 1 to 5, comprising, as component A) 4- [2-methyl-3- (4, 5- dihydroisoxazol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5- hydroxy-IH-pyrazole .
8. A synergistic herbicidal mixture as claimed in any of claims 1 to 7, comprising, two active ingredients, a 3-heterocyclyl- substituted benzoyl derivative of the formula I (component A) as claimed in claims 1 to 7 and the compound of formula II (component B) .
9. A synergistic herbicidal mixture as claimed in claim 8, comprising as component A) 4- [2-methyl-3- (4, 5-dihydroisoxa- zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-IH- pyrazole and as component B) the compound of formula II .
10. A synergistic herbicidal mixture as claimed in any of claims 1 to 7, comprising, at least three active ingredients, a 3- heterocyclyl-substituted benzoyl derivative of the formula I (component A) as claimed in claims 1 to 7, 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 .
11. A synergistic herbicidal mixture as claimed in claim 1 or 10 comprising, as component C) , at least one herbicidal compound from the groups CI to C16:
CI acetyl-CoA carboxylase inhibitors (ACC) : cyclohexenone oxime ethers, phenoxyphenoxypropionic esters or arylaminopropionic acids;
C2 acetolactate synthase inhibitors (ALS) : imidazolinones, pyrimidyl ethers, sulfonamides or sulfonylureas;
C3 amides; C4 auxin herbicides : pyridinecarboxylic acids, 2,4-D or benazolin;
C5 auxin transport inhibitors;
C6 carotenoid biosynthesis inhibitors;
C7 enolpyruylshikimate 3-phosphate synthase inhibitors (EPSPS) ;
C8 glutamine synthetase inhibitors;
C9 lipid biosynthesis inhibitors: anilides, chloroacetanilides, thioureas, benfuresate or perfluidone;
CIO mitosis inhibitors: carbamates, dinitroanilines, pyridines, butamifos, chlorthal-dimethyl (DCPA) or maleic hydrazide;
Cll protoporphyrinogen IX oxidase inhibitors: diphenyl ethers, oxadiazoles, cyclic imides or pyrazoles;
C12 photosynthesis inhibitors: propanil, pyridate, pyridafol; benzothiadiazinones/ dinitrophenols, dipyridylenes, ureas, phenols, chloridazon, triazines, triazinones, uracils or biscarbamates;
C13 synergists: oxiranes;
C14 growth substances: aryloxyalkanoic acids, benzoic acids or quinolinecarboxylic acids;
C15 cell wall synthesis inhibitors:
C16 various other herbicides: dichloropropionic acids, dihydrobenzofurans, phenylacetic acids or aziprotryn, barban, bensulide, benzthiazuron, benzofluor, buminafos, buthidazole, buturon, cafenstrole, chlorbufam, chlorofenprop-methyl, chloroxuron, cinmethylin, 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, sulfallate (CDEC) , terbuσarb, triazofenamide, triaziflam or trimeturon;
or their environmentally compatible salts.
12. A synergistic herbicidal mixture as claimed in claims 1 or 10, comprising, as component C) , at least one herbicidal compound from the groups CI to C16 :
CI acetyl-CoA carboxylase inhibitors (ACC) : cyclohexenone oxime ethers : alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, butroxydim, clefoxydim or tepraloxydim; phenoxyphenoxypropionic■-.esters-: 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- ethyl, isoxapyrifop, propaquizafop, quizalofop- ethyl, quizalofop-P-ethyl or quizalofop-tefuryl; or arylaminopropionic acids : flamprop-methyl or flamprop-isopropyl;
C2 acetolactate synthase inhibitors (ALS) : imidazolinones : imazapyr, imazaquin, imazamethabenz-methyl (imazame) , imazamoc, imazapic, imazethapyr or imazamethapyr; pyrimidyl ethers : pyrithiobac-acid, pyrithiobac-sodium, bispyribac- sodium, KIH-6127 or pyribenzoxym; sulfonamides : florasulam, flumetsulam or metosulam; or sulfonylureas : 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, triflusulf ron-methyl, N- [ [ [4-methoxy-6-
(trifluoromethyl) -1, 3,5-triazin-2-yl] amino] - ' carbonyl] -2- (trifluoromethyl) -benzenesulfonamide, sulfosulfuron or iodosulfuron;
C3 amides: allidochlor (CDAA) , benzoylprop-ethyl, bromobutide, chlorthiamid, diphenamid, etobenzanid (benzchlomet) , fluthiamide, fosamin or monalide;
C4 auxin herbicides: pyridi'ne carboxyIic~"ac!ids : clopyralid or picloram; or 2,4-D or benazolin;
C5 auxin transport inhibitors : naptalame or diflufenzopyr;
C6 carotenoid biosynthesis inhibitors: benzofenap, σlomazone (dimethazone) , diflufenican, fluorochloridone, fluridone, pyrazolynate, pyrazoxyfen, isoxaflutole, isoxachlortole, mesotrione, sulcotrione (chlormesulone) , ketospiradox, flurtamone, norflurazon or amitrol; C7 enolpyruvylshikimate-3-phosphate synthase inhibitors (EPSPS) : glyphosate or sulfosate;
C8 glutamine synthetase inhibitors : bilanafos (bialaphos) or glufosinate-ammonium;
C9 lipid biosynthesis inhibitors: anilides: anilofos or mefenacet; chloroacetanilides: dimethenamid, S-dimethenamid, acetochlor, alachlor, butachlor, butenachlor, diethatyl-ethyl, dimethachlor, metazachlor, metolachlor, S- metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor or xylachlor; ' thioureas : butylate, cycloate, di-allate, dimepiperate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb (benthiocarb) , tri-allate or vernolate; or benfuresate or perfluidone;
CIO mitosis inhibitors: - carbamates: asulam, carbetaitdd, - chlorprophara, orbencarb,- pronamid
(propyzamid) , propham or tiocarbazil; dinitroanilines : benefin, butralin, dinitramin, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine or trifluralin; pyridines : dithiopyr or thiazopyr; or butamifos, chlorthal-dimethyl (DCPA) or maleic hydrazide,-
Cll protoporphyrinogen IX oxidase inhibitors: diphenyl ethers : acifluorfen, acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP) , ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen or oxyfluorfen; oxadiazoles : oxadiargyl or oxadiazon; - cyclic imides: azafenidin, butafenacil, carfentrazone-ethyl, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, sulfentrazone or thidiazimin; or - pyrazoles:
ET-751, JV 485 or nipyraclofen;
hotosynthesis inhibitors : propanil, pyridate or pyridafol; - benzothiadiazinones: bentazone; ' dinitrophenols : bromofenoxim, dinoseb, dinoseb-acetate, dinoterb or
DNOC; - dipyridylenes: cyperquat-chloride, difenzoquat-methylsulfate, diquat or paraquat-dichloride; ureas: chlorbromuron, chlorotoluron, difenoxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron,
•isoprot-uron-,*. isquron-,-.-l-inuroai ■ . ethabenzthiazuron, methazole, metobenzuron, metoxuron, monolinuron, neburon, siduron or tebuthiuron; phenols : bromoxynil or ioxynil ; chloridazon; triazines : ametryn, atrazine, cyanazine , desmetryn, dimethamethryn, hexazinone, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbutryn, terbutylazine or trietazine ; triazinones : metamitron or metribuzine ; uracils : bromacil , lenacil or terbacil ; or biscarbamates : desmedipham or phenmedipham;
C13 synergists : - oxiranes : tridiphane;
C14 growth substances: aryloxyalkanoic acids : 2,4-DB, clomeprop, dichlorprop, dichlorprop-P (2,4-
DP-P) , fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, or triclopyr; benzoic acids : chloramben or dicamba; or - quinolinecarboxylic acids: quinclorac or quinmerac;
C15 cell wall synthesis inhibitors: isoxaben or dichlobenil;
C16 various other herbicides: dichloropropionic acids : dalapon; dihydrobenzofurans: ethofumesate; phenylacetic aeidsY chlorfenac (fenac) ; or aziprotryn, barban, bensulide, benzthiazuron, benzofluor, buminafos, buthidazole, buturon, cafenstrole, chlorbufam, chlorfenpro -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, sulfallate (CDEC) , terbucarb, triazofenamid, triaziflan or trimeturon; or their environmentally compatible salts.
13. A synergistic herbicidal mixture as claimed in 10, comprising, as component C) , at least one herbicidal compound from the groups C2, C6 or C 12 as defined in claim 12.
14. A synergistic herbicidal mixture as claimed in claim 10 comprising, as component A) 4- [2-methyl-3- (4, 5-dihydroisoxa- zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-lH- pyrazole, as component B) the compound of formula II and as component C) a herbicidal compound from the group C2.
15. A synergistic herbicidal mixture as claimed in claim 10 comprising, as component A) 4- [2-methyl-3- (4, 5-dihydroisoxa- ' zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-IH- pyrazole, as component B) the compound of formula II and as component C) a herbicidal compound from the group C6.
16. A synergistic herbicidal mixture as claimed in claim 10 comprising, as component A) 4- [2-methyl-3- (4, 5-dihydroisoxa- - zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-IH- pyrazole, as component B) the compound of formula II and as component C) isoxaflutole .
17. A synergistic herbicidal mixture as claimed in claim 10 comprising, as component' A) "4i-[2-methyl-3- (4, 5-dihydroisoxa- zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-IH- pyrazole, as component B) the compound of formula II and as component C) a herbicidal compound from the group C12.
18. A synergistic herbicidal mixture as claimed in claim 10 comprising, as component A) 4- [2-methyl-3- (4, 5-dihydroisoxa- zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-IH- pyrazole, as component B) the compound of formula II and as component C) a triazine from group C12 as defined in claim 12.
19. A synergistic herbicidal mixture as claimed in claim 8, comprising as component A) 4- [2-methyl-3- (4, 5-dihydroisoxa- zol-3-yl) -4-methylsulfonyl-benzoyl] -1-methyl-5-hydroxy-IH- pyrazole, as component B) the compound of formula II and as component C) atrazine.
20. A synergistic herbicidal mixture as claimed in claim 8, comprising as component A) 4- [2-methyl-3- (4,5-dihydroisoxa- zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-IH- pyrazole, as component B) the compound of formula II and as component C) bentazone.
21. A synergistic herbicidal mixture as claimed in claim 8, comprising as component A) 4- [2-methyl-3- (4,5-dihydroisoxa- zol-3-yl) -4-methylsulfonyl-benzoyl] -l-methyl-5-hydroxy-IH- pyrazole, as component B) the compound of formula II and as component C) pyridate.
22. A synergistic herbicidal mixture as claimed in any of claims 1 to 7rft comprising, at least three active ingredients, a 3- heterocyclyl-substituted benzoyl derivative of the formula I (component A) as claimed in claims 1 to 7, 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.
23-. A synergistic ■herbicidal--ιair.ture- as> claimed -in any of claims 1 to 7, comprising, at least three active ingredients, a 3- heterocyclyl-substituted benzoyl derivative of the formula I (component A) as claimed in claims 1 to 7, 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; and
D) a safening effective amount of at least one safener selected from the group of isoxadifen, mefenpyr and fenchlorazol .
24. Synergistic herbicidal mixture as claimed in any of claims 1 to 23, wherein component A) and B) are present in a weight ratio of 1:0.001 to 1:500.
25. Synergistic herbicidal mixture as claimed in any of claims 10 to 24, wherein component A) and component C) are present in a weight ratio of 1:0.002 to 1:800.
26. Synergistic herbicidal mixture as claimed in any of claims 10 to 25,rΛwherein component A) and component D) are present in a weight ratio of 1:0.002 to 1:800.
27. A herbicidal composition comprising a herbicidally active amount of a synergistic herbicidal mixture as claimed in any of claims 1 to 26, at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.
28. A process for the preparation of herbicidal compositions as claimed;.in-claim-27r.-,wherein.component Aj., .component B) , if . desired, component C) , if desired, component D) , at least one inert liquid and/or solid carrier and, if appropriate, a surfactant are mixed.
29. A method of controlling undesired vegetation, which comprises applying a synergistic herbicidal mixture as claimed in any of claims 1 to 26 before, during and/or after the emergence of undesired plants, it being possible for the herbicidally active compounds of components A) , B) , if desired, C) and, if desired, D) to be applied simultaneously or in succession.
30. A method of controlling undesired vegetation as claimed in claim 29, wherein the leaves of the crop plants and of the undesired plants are treated.
PCT/EP2003/007321 2002-07-08 2003-07-08 Synergistically acting herbicidal mixtures WO2004004463A1 (en)

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MXPA05000049A MXPA05000049A (en) 2002-07-08 2003-07-08 Synergistically acting herbicidal mixtures.
EP03740437A EP1521529B1 (en) 2002-07-08 2003-07-08 Synergistically acting herbicidal mixtures
DE60312864T DE60312864T2 (en) 2002-07-08 2003-07-08 SYNERGISTIC-ACTIVE HERBICIDES MIXTURES
YUP-1154/04A RS50941B (en) 2002-07-08 2003-07-08 Synergistically acting herbicidal mixtures
US10/519,978 US7632782B2 (en) 2002-07-08 2003-07-08 Synergistically acting herbicidal mixtures
BR0312497-5A BR0312497A (en) 2002-07-08 2003-07-08 Synergistic herbicidal mixture, herbicidal composition, process for preparing it, and method of controlling unwanted vegetation
JP2004518742A JP4739752B2 (en) 2002-07-08 2003-07-08 Synergistic herbicide mixture
CA2490499A CA2490499C (en) 2002-07-08 2003-07-08 Synergistically acting herbicidal mixtures
UAA200500947A UA81633C2 (en) 2002-07-08 2003-08-07 Herbicidal mixture and composition with synergic effect, a method for obtaining a herbicidal composition and a method for controlling undesirable vegetation
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