WO2011161131A1 - Herbicidal mixtures - Google Patents

Herbicidal mixtures Download PDF

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Publication number
WO2011161131A1
WO2011161131A1 PCT/EP2011/060389 EP2011060389W WO2011161131A1 WO 2011161131 A1 WO2011161131 A1 WO 2011161131A1 EP 2011060389 W EP2011060389 W EP 2011060389W WO 2011161131 A1 WO2011161131 A1 WO 2011161131A1
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group
salts
methyl
esters
compound
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PCT/EP2011/060389
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French (fr)
Inventor
Markus Gewehr
Matthias Pohlman
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Basf Se
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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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the present invention relates to mixtures comprising, as active compounds
  • non ACC herbicides namely benfuresate, butylate, cycloate, dalapon, dime- piperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate; b2) the group of the ALS inhibitors selected from the group consisting of
  • sulfonylureas selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethox- ysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl- sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodo- sulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, metsulfu- ron, metsulfuron-methyl, nicosulfuron, orthosulfamuron,
  • imidazolinones selected from the group consisting of imazamethabenz, ima- zamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and
  • triazolopyrimidine herbicides and sulfonamides selected from the group consisting of cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam,
  • pyrimidinylbenzoates selected from the group consisting of bispyribac, bispyri- bac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithio- bac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2- pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1 -methylethyl ester (CAS 420138-41 -6), 4-[[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]- benzoic acid propyl ester (CAS 420138-40-5) and N-(4-bromophenyl)-2-[(4,6- dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01 -8) and sulfonylamino
  • the group of the photosynthesis inhibitors selected from the group consisting of arnica rbazone,
  • inhibitors of the photosystem II selected from the group consisting of triazine herbicides, including chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, des- metryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, propazin, simazin, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin,
  • triazine herbicides including chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, des- metryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, prop
  • aryl urea compounds such as chlorobromuron, chlorotoluron, chloroxuron, dime- furon, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, metha- benzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, te- buthiuron and thiadiazuron,
  • phenyl carbamates such as desmedipham, karbutilat, phenmedipham and phenmedipham-ethyl
  • nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters,
  • uraciles such as bromacil, lenacil and terbacil
  • the group of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, ben- zfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlometh- oxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumi- clorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, flu- thiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluor- fen, pentoxazone, profluazol,
  • PDS inhibitors selected from the group consisting of beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, and 4-(3- trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33- 7),
  • HPPD inhibitors selected from the group consisting of benzobicyclon, ben- zofenap, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sul- cotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone, and bleacher, unknown target selected from the group consisting of aclonifen, ami- trole, clomazone and flumeturon;
  • the group of the glutamine synthase inhibitors selected from the group consisting of bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and ist salts, in particular glufosinate-P or glufosinate-ammonium;
  • the group of the mitose inhibitors selected from the group consisting of compounds of group K1 selected from the group consisting of dinitroanilines such as benflu- ralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin,
  • phosphoramidates such as amiprophos, amiprophos-methyl and butamiphos, benzoic acid herbicides such as chlorthal and chlorthal-dimethyl,
  • pyridines such as dithiopyr and thiazopyr
  • benzamides such as propyzamide and tebutam
  • chloroacetamides such as acetochlor, alachlor, butachlor, dimethachlor, di- methenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethox- amid, pretilachlor, propachlor, propisochlor and thenylchlor,
  • oxyacetanilides such as flufenacet and mefenacet
  • acetanilides such as diphenamid, naproanilide and napropamide
  • tetrazolinones such as fentrazamide, and other herbicides such as anilofos, cafenstrole, fenoxasulfone, ipfencarba- zone, piperophos and pyroxasulfone;
  • cellulose biosynthesis inhibitors selected from the group consisting of chlorthiamid, dichlobenil, flupoxam, isoxaben, 1 -cyclohexyl-5- pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3-ylamine and piperazine compounds of formula III,
  • A is phenyl or pyridyl where R a is attached in the ortho-position to the point of attachment of A to a carbon atom;
  • Ry is d-Ce-alkyl, C 3 -C 4 -alkenyl, C 3 -C 4 -alkynyl, NR A R B or Ci-C 4 -haloalkyl and q is 0, 1 or 2;
  • R A ,R B independently of one another are hydrogen, Ci-C6-alkyl, C3-C6- alkenyl and C3-C6-alkynyl; together with the nitrogen atom to which they are attached, R A , R B may also form a five- or six-membered saturated, partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S, which ring may be substituted by 1 to 3 groups R aa ;
  • D is a covalent bond or Ci-C 4 -alkylene
  • R a1 is hydrogen, OH, Ci-C 8 -Alkyl, Ci-C 4 -haloalkyl, C 3 -C 6 -cycloalkyl;
  • R b independently of one another is CN, NO2, halogen, Ci-C 4 -alkyl, Ci-C 4 - haloalkyl, C2-C 4 -alkenyl, C3-C6-alkynyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, ben-
  • R b together with the group R a or R b attached to the adjacent ring atom may also form a five- or six-membered saturated or partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S, which ring may be partially or fully substituted by R aa ;
  • p is 0 or1 ;
  • R 40 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; where in groups R 30 , R a and their sub-substituents the carbon chains and/or the cyclic groups may carry 1 , 2, 3 or 4 substituents R aa and/or R a1 ;
  • R 31 is Ci-C 4 -alkyl
  • R 25 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-halo-alkoxy
  • R 33 is hydrogen, or R 33 and R 34 together are a covalent bond
  • R 34 , R 35 , R 36 , R 37 independently of one another are hydrogen;
  • R 38 , R 39 independently of one another are hydrogen, halogen or OH;
  • the group of the decoupler herbicides selected from the group consisting of di- noseb, dinoterb and DNOC and its salts;
  • the group of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, 2,4-DB and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, bena- zolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr and its salts or esters, MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,
  • auxin transport inhibitors selected from the group consisting of diflufenzopyr and its salts, naptalam and its salts;
  • the group of the other herbicides selected from the group consisting of bromobu- tide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazo- met, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flam- prop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosa- mine, fosamine-ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl- dymron,
  • the mixture of the present invention generally includes the at least one compound I and the compound II in synergistically effective amounts.
  • the mixtures of the present invention will have herbicide action due to the presence of the compound I as well as insecticide, acaricide or nematicide action due to the presence of the compound II.
  • the mixture of the present invention generally leads to a synergism between the at least one compound I and the compound II.
  • Synergism in terms of the present invention means that the use of the inventive mixture leads to an effect which surpasses the additive effect (in mathematical terms) of the compounds I and II, when applied indi- vually.
  • the term "in synergistically effective amounts” refers to the fact that the purely additive effect (in mathematical terms) of the application of the individual compounds is surpassed by the application of the inventive mixture.
  • the health of a plant is increased synergistically.
  • in synergistically effective amounts refers to the fact that the purely additive effect (in mathematical terms) of the application of the individual compounds is surpassed by the application of the inventive mixture.
  • the synergistic increase of the health of a plant is more than surprising, since it can be assumed that nematicidal compounds and herbicides have completely different mode of actions.
  • effective amount denotes an amount of the inventive mixtures, which is sufficient for achieving the synergistic plant health effects, in particular the plant health effects as defined herein, especially the yield effects as defined herein. More exemplary information about amounts, ways of application and suitable ratios to be used is given below.
  • the present invention also relates to a method for increasing the health of a plant, in particular in a synergistic manner, in particular the yield of a plant, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with a effective amount, in particular with a synergistically effective amount, of a mixture as defined above.
  • the respective compounds I can also be used as in their form as agriculturally acceptable salts and esters.
  • suitable salts include those salts, where the counterion is an agri- culturally acceptable cation or anion.
  • suitable agriculturally acceptable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium substituted ammonium (hereinafter also termed as organoam- monium) in which one to four hydrogen atoms are replaced by Ci-C4-alkyl, hydroxy-Ci- C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diiso
  • Suitable agriculturally acceptable anions are in particular the halogenides, especially the chlorides, the nitrates, sulfates, hydrogensulfates, phosphates, hydrogenphos- phates, ammoniumhydrogenphosphates, borates including orthoborates and metabo- rates such as diborates and pentaborates, formiates, acetates, propionates etc.
  • Suitable ester include the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n- pentyl, n-hexyl, isooctyl, 2-methoxylethyl, 2-ethoxyethyl, 1 -methyl-2-butoxyethyl (bu- tometyl), 2-butoxyethyl (butotyl), 3-butoxypropyl, 2-butoxypropyl, 2-ethylhexyl and mexyl (1 -methylhexyl) esters.
  • suitable salts of dicamba are dicamba-sodium, dicamba-potassium, dicamba-methylammonium, dicamba-dimethylammonium, dicamba- isopropylammonium, dicamba-diglycolamine, dicamba-olamine, dicamba-diolamine and dicamba-trolamine.
  • suitable ester are dicamba-methyl and dicamba-butoyl.
  • Suitable salts of 2,4-D are 2,4-D dimethylammonium, 2,4-D diethanolammonium, 2,4-D triethanolammonium, 2,4-D triisopropanolammonium, 2,4-D sodium; 2,4-D isopropylammonium.
  • Examples of a suitable ester of 2,4-D are 2,4-D-butotyl, 2,4-D-butyl, 2,4- D-ethyl, 2,4-D-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl.
  • Suitable salts of 2,4-DB are for example 2,4-DB sodium, 2,4-DB potassium and 2,4-DB dimethylammonium.
  • Suitable salts of dichlorprop are for example dichlorprop potassium and dichlorprop dimethylammonium.
  • Examples of a suitable ester of dichlorprop are dichlorprop-butotyl and dichlorprop-isoctyl.
  • Suitable salts and esters of MCPA include MCPA-butotyl, MCPA-butyl, MCPA- dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-thioethyl, MCPA-2- ethylhexyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA- olamine, MCPA-potassium, MCPA-sodium and MCPA-trolamine.
  • MCPB is MCPB sodium.
  • a suitable ester of MCPB is MCPB-ethyl.
  • Suitable salts of clopyralid are clopyralid potassium, clopyralid olamine and clopyralid triisopropanolammonium.
  • Examples of a suitable ester of fluroxypyr are fluroxypyr-meptyl and fluroxypyr-2- butoxy-1 -methylethyl, wherein fluroxypyr-meptyl is preferred.
  • Suitable salts of picloram are picloram dimethylammonium, picloram potassium, piclo- ram triisopropanolammonium, picloram triisopropylammonium and picloram trolamine.
  • a suitable ester of picloram is picloram-isoctyl.
  • a suitable salt of triclopyr is triclopyr triethalammonium.
  • a suitable ester of triclopyr is triclopyr-butotyl.
  • Suitable salts and esters of chloramben include chloramben-ammonium, chloramben- diolamine, chloramben-methyl, chloramben-methylammonium and chloramben-sodium.
  • Suitable salts and esters of 2,3,6-TBA include 2,3,6-TBA-dimethylammonium, 2,3,6- TBA-lithium, 2,3,6-TBA-potassium and 2,3,6-TBA-sodium.
  • Suitable salts and esters of aminopyralid include aminopyralid-potassium and amino- pyralid-tris(2-hydroxypropyl)ammonium.
  • Suitable salts of glyphosate are for example glyphosate-ammonium, glyphosate- diammonium, glyphoste-dimethylammonium, glyphosate-isopropylammonium, gly- phosate-potassium, glyphosate-sodium, glyphosate-trimesium as well as the etha- nolamine and diethanolamine salts, preferably glyphosate-diammonium, glyphosate- isopropylammonium and glyphosate-trimesium (sulfosate).
  • Suitable salts of glufosinate are for example glufosinate-ammonium and glufosinate-P.
  • Suitable salts and esters of bromoxynil are for example bromoxynil butyrate, bro- moxynil heptanoate, bromoxynil octanoate, bromoxynil potassium and bromoxynil sodium;
  • Suitable salts of ioxonil are for example ioxonil-octanoate, ioxonil-potassium and ioxo- nil-sodium.
  • Suitable salts and esters of mecoprop include mecoprop-butotyl, mecoprop- dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-2-ethylhexyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-potassium, mecoprop-sodium and me- coprop-trolamine.
  • Suitable salts of mecoprop-P are for example butotyl, dimethylammonium, ethylhexyl, potassium and sodium
  • Suitable salts of diflufenzopyr is diflufenzopyr-sodium.
  • Suitable salts of naptalam is naptalam -sodium.
  • Suitable salts of DNOC are for example DNOC-ammonium, DNOC-potassium and DNOC-sodium
  • Suitable salts and esters of 2,4-DB are for example 2,4-DB-butylester, 2,4-DB- dimethylammonium, 2,4-DB-triisopropanolammonium, 2,4-DB-isoctyl, 2,4-DB- potassium and 2, 4-DB-sodium
  • Suitable salts of aminocyclopyrachlor are for example aminocyclopyrachlor dimethyl- ammonium, aminocyclopyrachlor triisopropanolammonium, aminocyclopyrachlor sodium and aminocyclopyrachlor potassium
  • the compound II of formula II which has the IPAC name [(3S,4R,4aR,6S,6aS,12R,
  • Healthier plants are desirable since they result among others in better yields and/or a better quality of the plants or crops. Healthier plants also better resist to biotic and/or abiotic stress. A high resistance against biotic stresses in turn allows the person skilled in the art to reduce the quantity of pesticides applied and consequently to slow down the development of resistances against the respective pesticides.
  • these objects are in part or in whole achieved by using the mixtures as defined in the outset.
  • Preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b1 ) the group of the lipid biosynthesis inhibitors, wherein in this group, preference is given to compounds selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P- butyl, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalo- fop-P-ethyl, quizalofop-P-
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors, wherein in this group, preference is given to the compounds selected from the group consisting of
  • sulfonylureas in particular those selected from the group consisting of amidosul- furon, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cyclo- sulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfu- ron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazosul- furon, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl,
  • Preferred mixtures of the invention are also mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors, selected from the group consisting of
  • imidazolinones selected from the group consisting of imazamethabenz, ima- zamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors, selected from the group consisting of
  • the triazolopyrimidine herbicides and sulfonamides selected from the group con- sisting of diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam and Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors selected from the group consisting of
  • pyrimidinylbenzoates selected from the group consisting of bispyribac- sodium, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, flucar- apelone-sodium, propoxycarbazon- sodium and thiencarbazone-methyl.
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein compound (I) is selected from the group b3), i.e. the group of the photosynthesis inhibitors (group b4), wherein in this group, preference is given to the compounds selected from the group consisting of amicarbazone, ametryn, atrazine, chloridazone, cyanazine, hexazinone, metribuzin, simazin, terbuthy- lazin and terbutryn, and wherein in this group is likewise preference is given to the compounds selected from the group consisting of the aryl ureas such as chlorotoluron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron and thiadiazuron, the phenyl carbamates desmedipham, karbutilat or phenmedipham, bromoxynil and its salts and esters,
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the protoporphyrinogen-IX oxidase inhibitors (group b4), wherein in this group, preference is given acifluorfen, acifluorfen-sodium, bencarbazone, ben- zfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, cinidon-ethyl, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fomesafen, lacto- fen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraflufen-ethyl, saflufenacil, sulfentra
  • Preferred mixturesof the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the bleacher herbicides (group b5), wherein in this group, preference is given to the PDS inhibitors diflufenican, flurochloridone and picolinafen, to the HPPD inhibi- tors benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone and to the bleachers aclonifen, amitrole, clomazone and flumeturon.
  • group b5 group of the bleacher herbicides
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein compound (I) is selected from the group b6), i.e. the group of the EPSP synthase inhibitors, wherein in this group, preference is given to glyphosate and its salts.
  • Preferred mixtures are mixtures comprising compound I and compound II, wherein compound (I) is selected from b7) the group of the glutamine synthase inhibitors, wherein in this group, preference is given to glufosinate, and its salts.
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b9), i.e. the group of the mitose inhibitors, wherein in this group, preference is given to thedinitroanilines, in particular benfluralin, ethalfluralin, oryzalin, pendi- methalin and trifluralin, and the pyridines, in particular dithiopyr and thiazopyr.
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10), i.e. the group of the VLCFA inhibitors, wherein in this group, preference is given to the chloroacetamides, which are in particular selected from the group con- sisting of acetochlor, alachlor, butachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pretilachlor and thenylchlor, to the the oxyacetanilides which are in particular selected from the group consisting of flufenacet and mefenacet, to the tetrazolinone fentrazamide, and to the compounds selected from the group consisting of cafenstrole, fenoxasulfone, ipfencarbazone andpyroxasulfone.
  • the group b10 i.e. the group of the
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b1 1 ), i.e. the group of the cellulose biosynthesis inhibitors, wherein in this group, preference is given to isoxaben and 1 -cyclohexyl-5-pentafluorphenyloxy-14- [1 ,2,4,6]thiatriazin-3-ylamine.
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the compounds of the general formula III.
  • Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b13), i.e. the group of the auxin herbicides, wherein in this group, preference is given to 2,4-D and its salts and esters, aminopyralid, clopyralid and its salts and es- ters, dicamba and its salts and esters, fluroxypyr and its salts or esters, MCPA and its salts and esters, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, triclopyr and its salts and esters and aminocyclopyrachlor and its salts and esters.
  • the group b13 i.e. the group of the auxin herbicides, wherein in this group, preference is given to 2,4-D and its
  • Preferred mixtures of the invention are also mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from the group b14), i.e. the group of the auxin transport inhibitors, wherein in this group, preference is given to diflufenzopyr, and its salts.
  • Preferred mixtures of the invention are also mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from group b15), wherein in this group, preference is given to cinmethylin, dymron, indano- fan, indaziflam, oxaziclomefone and triaziflam.
  • More preferred mixtures of the invention are mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from the group b1 ), i.e. the group of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, fenoxaprop- P-ethyl, fluazifop-P-butyl, haloxyfop-P-methyl, pinoxaden, profoxydim, sethoxydim, te- praloxydim and tralkoxydim, esprocarb, prosulfocarb, thiobencarb and triallate.
  • the group lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-but
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b2), i.e. the group of the ALS inhibitors, where the ALS inhibitors are selected from the group consisting of the sulfonylureas bensulfuron-methyl, chlori- muron-ethyl, cyclosulfamuron, flupyrsulfuron-methyl-sodium, foramsulfuron, iodosulfu- ron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, nicosulfuron, pyrazo- sulfuron-ethyl, rimsulfuron, sulfosulfuron, and tritosulfuron,
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b2), i.e. the group of the ALS inhibitors, where the the ALS inhibitors are selected from the group of the imidazolinones imazamethabenz, imazamethabenz- methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr and their salts.
  • the group of the ALS inhibitors where the the ALS inhibitors are selected from the group of the triazolopyrimidine herbicides and sulfonamides, which are selected from the group consisting of diclosulam, flumetsulam, florasulam, penox- sulam and pyroxsulam.
  • the ALS inhibitors are selected from the group of the triazolopyrimidine herbicides and sulfonamides, which are selected from the group consisting of diclosulam, flumetsulam, florasulam, penox- sulam and pyroxsulam.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b2), i.e.
  • the group of the ALS inhibitors where the ALS inhibitors are selected from the group of the pyrimidinylbenzoates bispyribac-sodium, pyribenzoxim, pyriftalid, propoxycarbazon- sodium and thiencarbazone-methyl.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from group b3), i.e. the group of the photosynthesis inhibitors selected from the group consisting of ametryn, atrazine, cyanazine, hexazinone, metribuzin, simazin, terbuthy- lazin and terbutryn.
  • group b3 i.e. the group of the photosynthesis inhibitors selected from the group consisting of ametryn, atrazine, cyanazine, hexazinone, metribuzin, simazin, terbuthy- lazin and terbutryn.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the b4) protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, acifluorfen-sodium, flumioxazin, fomesafen, lactofen, oxyfluorfen, saflufenacil, sulfentrazone, ethyl [3-[2-chloro-4-fluoro-5-(1 -methyl-6- trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2- pyridyloxy]acetate, 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H- benzo[1 ,4]oxazin-6-yl
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the b5) bleacher herbicides, which are selected from the group consisting of diflufenican, flurochloridone and picolinafen,
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the b5) bleacher herbicides, which are selected from the group of the HPPD inhibitors: benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b6) of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b7) of the glutamine synthase inhibitors selected from the group consisting of glufosinate and its salts.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b9) of the mitose inhibitors selected from the group consisting of the dinitroanilines, in particular from the group consisting of pendimethalin and trifluralin.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10) of the VLCFA inhibitors consisting of the chloroacetamides ace- tochlor, dimethenamid-P, metazachlor, metolachlor, metolachlor-S and pretilachlor and the oxyacetanilides flufenacet and mefenacet and the tetrazolinone fentrazamide.
  • VLCFA inhibitors consisting of the chloroacetamides ace- tochlor, dimethenamid-P, metazachlor, metolachlor, metolachlor-S and pretilachlor and the oxyacetanilides flufenacet and mefenacet and the tetrazolinone fentrazamide.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b 1 1 ) of the cellulose biosynthesis inhibitors selected from the group consisting of isoxaben and 1 -cyclohexyl-5-pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3- ylamine.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b 1 1 ) of the cellulose biosynthesis inhibitors selected from the group of the compounds of the formula III.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b13) of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, aminopyralid and its salts, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr-meptyl, MCPA, MCPB and its salts and esters, mecoprop and its salts and esters, quinclorac and quinmerac.
  • the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, aminopyralid and its salts, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr-meptyl, MCPA, MCPB and its salts and esters, mecoprop and its salts and esters, quinclorac and quinmerac.
  • mixtures of the invention are mixtures comprising a compound I and the compound II, wherein the compound (I) is the b14) the auxin transport inhibitor diflufenzopyr. Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from group b15) consisting of cinmethylin, dymron, indanofan, indaziflam, oxaziclome- fone and triaziflam.
  • Most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b1 ) of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, pinoxaden, profoxydim, sethoxydim, te- praloxydim and tralkoxydim.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the ALS inhibitors b2) selected from the group consisting of the sul- fonylureas chlorimuron-ethyl, foramsulfuron, nicosulfuron, rimsulfuron and tritosulfuron,
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the ALS inhibitors b2) selected from the group consisting of the imi- dazolinones imazamox, imazapic, imazapyr, imazaquin and imazethapyr and their salts.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the ALS inhibitors b2) selected from the group consisting of the pyrimidinylbenzoates pyribenzoxim and pyriftalid.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b3) of the photosynthesis inhibitors selected from the group consisting of ametryn, atrazine, cyanazine, simazin and terbuthylazin.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b4) of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, flumioxazin, fomesafen, saflufenacil and sulfentrazone.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b5) of the bleacher herbicides, selected from the group consisting of the PDS diflufenican, flurochloridone and picolinafen, Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b5) of the bleacher herbicides, selected from the group consisting ofthe HPPD inhibitors: benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tembotrione and topramezone.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the bleacher clomazone.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b6) of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is the the mi- tose inhibitor pendimethalin. Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10) of the VLCFA inhibitors selected from the group consisting of the chloroacetamides acetochlor, dimethenamid-P, metazachlor, metolachlor, metolachlor- S and pretilachlor.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10) of the VLCFA inhibitors selected from the group consisting of the oxyacetanilide flufenacet and the tetrazolinone fentrazamide.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b13) of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, clopyralid and its salts and esters, dicamba and its salts and esters, MCPA, quinclorac and quinmerac.
  • the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, clopyralid and its salts and esters, dicamba and its salts and esters, MCPA, quinclorac and quinmerac.
  • mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is indaziflam.
  • M-1 compound II and clethodim
  • M-2 compound II and clodinafop-propargyl
  • M-3 compound II and cycloxydim
  • M-4 compound II and pinoxaden
  • M-5 compound II and nicosulfuron
  • M-6 compound II and tritosulfuron
  • M-7 compound II and ima- zamox
  • M-8 compound II and imazapic
  • M-9 compound II and imazaquin
  • M-10 compound II and imazethapyr
  • M-1 1 compound II and pyribenzoxim
  • M-12 compound II and pyriftalid
  • M-13 compound II and atrazine
  • M-14 compound II and si- mazin
  • M-15 compound II and terbuthylazin
  • M-16 compound II and diuron
  • M-17 compound II and isoproturon
  • M-18 compound II and bro
  • the ratios by weight for the respective mixtures, in particular the binary mixtures, comprising the at least one compound I and the compound II are from from 1 :200 to 200:1 , in particular from 1 :100 to 100:1 or from 1 :50 to 50:1 , wherein the weight ratio of com- pound I is calculated as the free acid.
  • the mixtures of the invention may be binary mixtures comprising one compound I and the compound II.
  • the mixtures of the invention may also be mixtures comprising more than one compound I, e.g. 2, 3 or 4 compounds I, and the compound II.
  • the inventive mixtures can further contain one or more insecticides, fungicides, herbi- cides and plant growth regulators.
  • the present invention relates to a method for increasing the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with an effective amount of an inven- tive mixture.
  • the present invention relates to a method for increasing the yield of a plant, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with an effective amount of an inventive mixture.
  • the present invention relates to a method of increasing the health of a plant by treating plants, parts of such plants or at their locus of growth with an effective amount of inventive mixture. In a further more preferred embodiment, the present invention relates to a method of increasing the yield of a plant by treating plants, parts of such plants or at their locus of growth with an effective amount of inventive mixture.
  • the compounds contained in the mixtures as defined above can be applied simultane- ously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • applying the compound I and compound II is to be understood to denote, that at least the compound I and compound II occur simultaneously at the site of action (i.e. plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow) in an effective amount.
  • site of action i.e. plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow
  • the weight ratio of the compounds generally depends from the properties of the compounds of the inventive mixtures.
  • the compounds of the inventive mixtures can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
  • kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition.
  • kits may include the compound I and compound II and/or an adjuvant component and/or a further pesticidal compound (e.g. insecticide, fungicide or herbicide) and/or a growth regulator component).
  • a further pesticidal compound e.g. insecticide, fungicide or herbicide
  • One or more of the components may already be combined together or p re-formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or can- ister. In other embodiments, two or more components of a kit may be packaged separately, i.
  • kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition.
  • a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane.
  • the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquid or the agrochemical composition according to the invention is thus obtained.
  • 50 to 500 liters of the ready-to-use spray liquid are applied per hectare of agricultural useful area, preferably 50 to 400 liters.
  • individual compounds of the inventive mixtures formulated as composition (or formulation) such as parts of a kit or parts of the inventive mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
  • either individual compounds of the inventive mixtures formulated as composition or partially premixed components e.g. components comprising the compound I and compound II may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
  • either individual components of the composition according to the invention or partially premixed components, e. g. components comprising the compound I and compound II , can be applied jointly (e. .g. after tankmix) or consecutively.
  • the term yield refers to fruits in the proper sense, vegetables, nuts, grains and seeds.
  • plants generally comprises all plants of economic importance and/or men- grown plants. They are preferably selected from agricultural, silvicultural and ornamen- tal plants, more preferably agricultural plants and silvicultural plants, utmost preferably agricultural plants.
  • plant (or plants) is a synonym of the term “crop” which is to be understood as a plant of economic importance and/or a men-grown plant.
  • plant as used herein includes all parts of a plant such as germinating seeds, emerging seedlings, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.
  • the plants to be treated according to the invention are selected from the group consisting of agricultural, silvicultural, ornamental and horticultural plants more preferably from agricultural plants.
  • the plant to be treated according to the method of the invention is a horticultural plant.
  • the term "horticultural plants” are to be understood as plants which are commonly used in horticulture - e.g. the cultivation of ornamentals and/or fruits.
  • ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce.
  • fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
  • the plant to be treated according to the method of the invention is an ornamental plant.
  • Ornamental plants are plants which are commonly used in gar- dening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • the plant to be treated according to the method of the invention is a silvicultural plants.
  • the term "silvicultural plant” is to be understood as trees, more specifically trees used in reforestation or industrial plantations.
  • Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes.
  • Examples for silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm and oak.
  • the plant to be treated according to the method of the invention is an agricultural plant.
  • Agricultural plants are plants of which a part or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds.
  • Agricultural plants also include the horticultural plants fruits and vegetables.
  • the term agricultural plants include cereals, e.g. wheat, rye, barley, triticale, oats, sorghum or rice; beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • the plants to be treated in accordance with the method of the present invention are agricultural plants. All of the above-mentioned plants may be also modified plants, which have been modified by breeding, mutagenesis or genetic engineering (transgenic and non-transgenic plants). Genetically modified plants are plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that it cannot readily be obtained by cross breeding under natural circumstances, mutations or natural recombina- tion.
  • Plants as well as the propagation material of said plants, which can be treated with the inventive mixtures include all modified non-transgenic plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.
  • mixtures according to the present invention can be applied (as seed treatment, foliar spray treatment, in-furrow application or by any other means) also to plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf.
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s), oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated or farnesy- lated moieties or PEG moieties.
  • Plants that have been modified by breeding, mutagenesis or genetic engineering, e.g. have been rendered tolerant to applications of specific classes of herbicides can be obtained by creating insensitivity at the site of action of the herbi- cide by expression of a target enzyme which is resistant to herbicide; rapid metabolism (conjugation or degradation) of the herbicide by expression of enzymes which inactivate herbicide; or poor uptake and translocation of the herbicide.
  • Examples are the expression of enzymes which are tolerant to the herbicide in comparison to wild type enzymes, such as the expression of 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS), which is tolerant to glyphosate (see e.g.
  • EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
  • Zea mays with chimeric gene sequences coging for HDDP see e.g. W01996/38567, WO 2004/55191 ); Arabidopsis thaliana which is resistant to protox inhibitors (see e.g. US2002/0073443).
  • CB/LL/RW® (Syngenta) with tolerance to glufosinate; the soybean varieties “Roundup Ready® Soybean” (Monsanto) and “Optimum GAT®” (DuPont, Pioneer) with tolerance to glyphosate; the cotton varieties “Roundup Ready® Cotton” and “Roundup Ready Flex®” (Monsanto) with tolerance to glyphosate; the cotton variety "FiberMax Liberty Link®” (Bayer) with tolerance to glufosinate; the cotton variety “BXN®” (Calgene) with tolerance to bromoxynil; the canola varieties ..Navigator® “ und ..Compass® " (Rhone- Poulenc) with bromoxynil tolerance; the canola varierty"Roundup Ready® Canola” (Monsanto) with glyphosate tolerance; the canola variety "InVigor®” (Bayer) with glu- fosinate
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ - endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e.g. Photorhabdus spp.
  • VIP vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capa- ble of synthesizing such toxins are disclosed, e.g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e.g. EP-A 392225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e.g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis-related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e.g. potato cultivars capable of
  • plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e.g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e.g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rape, DOW Agro Sciences, Canada).
  • a modified amount of substances of content or new substances of content specifically to improve human or animal nutrition, e.g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e.g. potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e.g. potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).
  • Preferred modified plants suitable to be used in the methods of the present invention are those, which are rendered tolerant to the herbicide, which is compound II (includ- ing, but not limited to the above-referred plants) in accordance with the preferences within the inventive mixtures as set forth above.
  • preferred plants are those, which are resistant to glyphosate, glyphosinate, dicamba and imidazolinones.
  • Preferred agricultural plants are field crops, sugar beets, cereals such as wheat, rye, barley, triticale, oats, sorghum, rice, corn, cotton, rape, sunflowers, oilseed rape, juncea and canola, vine, legumes such as soybeans, peas and beans (fieldbeans), lentil, sugar cane, turf; ornamentals; vegetables, such as vegetables, such as cucumbers, leeks, paprika spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits (squashes, cucumber or melons ); alfalfa, clover and fruits, such as pomes, stone fruits or soft fruits, e.g.
  • More preferred agricultural plants are selected from soybean, wheat, sunflower, canola, oilseed rape, corn, cotton, sugar cane, juncea, peas, lentils, alfalfa, vine, and fruits (as defined above) and vegetables as defined above). Most preferred agricultural plants are selected from wheat, barley, corn, soybean, rice, canola, sunflower and fruits (as defined above) and vegetables as defined above). The utmost preferred plants are soybean, vine, and fruits (as defined above) and vegetables as defined above).
  • locus is to be understood as any type of environment, soil, area or material where the plant is growing or intended to grow as well as the environmental conditions (such as temperature, water availability, radiation) that have an influence on the growth and development of the plant and/or its propagules.
  • mixture means a combination of at least two active ingredients (compounds).
  • a mixture used for increasing the health of a plant comprises one compound (I) and one compound (II) or one compound (I) and one compound (II).
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This in- eludes seeds, grains, roots, fruits, tubers, bulbs, rhizomes, cuttings, spores, offshoots, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil, meristem tissues, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained.
  • vegetative plant material such as cuttings and tubers (e.g. potatoes)
  • propagules or "plant propagules” is to be understood to denote any structure with the capacity to give rise to a new plant, e.g. a seed, a spore, or a part of the vegetative body capable of independent growth if detached from the parent.
  • the term “propagules” or “plant propagules” denotes for seed.
  • health of a plant or "plant health” is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as increased yield, plant vigor, quality and tolerance to abiotic and/or biotic stress. It has to be emphasized that the above mentioned effects of the inventive mixtures, i.e. enhanced health of the plant, are also present when the plant is not under biotic stress and in particular when the plant is not under pest pressure.
  • "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the inventive mixture.
  • Increased yield can be characterized, among others, by the following improved properties of the plant: increased plant weight; and/or increased plant height; and/or increased biomass such as higher overall fresh weight (FW); and/or increased number of flowers per plant; and/or higher grain and/or fruit yield ; and/or more tillers or side shoots (branches); and/or larger leaves; and/or increased shoot growth; and/or increased protein content; and/or increased oil content; and/or increased starch content; and/or increased pigment content; and/or increased chlorophyll content (chlorophyll content has a positive correlation with the plant's photosynthesis rate and accordingly, the higher the chlorophyll content the higher the yield of a plant)
  • Gram and “fruit” are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant.
  • the yield is increased by at least 4 %, preferable by 5 to 10 %, more preferable by 10 to 20 %, or even 20 to 30 %. In general, the yield increase may even be higher.
  • the plant vigor becomes manifest in several aspects such as the general visual appearance.
  • Improved plant vigor can be characterized, among others, by the following improved properties of the plant: improved vitality of the plant; and/or improved plant growth; and/or improved plant development; and/or improved visual appearance; and/or improved plant stand (less plant verse/lodging); and/or improved emergence; and/or en- hanced root growth and/or more developed root system; and/or enhanced nodulation, in particular rhizobial nodulation; and/or bigger leaf blade; and/or bigger size; and/or increased plant height; and/or increased tiller number; and/or increased number of side shoots; and/or increased number of flowers per plant; and/or increased shoot growth; and/or enhanced photosynthetic activity (e.g.
  • Another indicator for the condition of the plant is the "quality" of a plant and/or its products.
  • enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the mixtures of the present invention.
  • Enhanced quality can be characterized, among others, by following improved properties of the plant or its product: increased nutrient content; and/or in- creased protein content; and/or increased content of fatty acids; and/or increased metabolite content; and/or increased carotenoid content; and/or increased sugar content; and/or increased amount of essential amino acids; and/or improved nutrient composition; and/or improved protein composition; and/or improved composition of fatty acids; and/or improved metabolite composition; and/or improved carotenoid composition; and/or improved sugar composition; and/or improved amino acids composition ; and/or improved or optimal fruit color; and/or improved leaf color; and/or higher storage capacity; and/or higher processability of the harvested products.
  • Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors.
  • Biotic and abiotic stress can have harmful effects on plants. Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes.
  • "enhanced tolerance or resistance to biotic and/or abiotic stress factors” means (1 .) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with an inventive mixture and (2.) that the negative effects are not diminished by a direct action of the inventive mixture on the stress factors, e.g.
  • Biotic stress can be caused by living organisms, such as competing plants (for example weeds), microorganisms (such as phythopathogenic fungi and/or bacteria) and/or viruses.
  • Negative factors caused by abiotic stress are also well-known and can often be observed as reduced plant vigor (see above), for example: dotted leaves, "burned leaves", reduced growth, less flowers, less biomass, less crop yields, reduced nutritional value of the crops, later crop maturity, to give just a few examples.
  • Abiotic stress can be caused for example by: extremes in temperature such as heat or cold (heat stress / cold stress); and/or strong variations in temperature; and/or temperatures unusual for the specific season; and/or drought (drought stress); and/or extreme wetness; and/or high salinity (salt stress); and/or radiation (for example by increased UV radiation due to the decreasing ozone layer); and/or increased ozone levels (ozone stress); and/or organic pollution (for example by phythotoxic amounts of pesticides); and/or inorganic pollution (for example by heavy metal contaminants).
  • extremes in temperature such as heat or cold (heat stress / cold stress); and/or strong variations in temperature; and/or temperatures unusual for the specific season; and/or drought (drought stress); and/or extreme wetness; and/or high salinity (salt stress); and/or radiation (for example by increased UV radiation due to the decreasing ozone layer); and/or increased ozone levels (ozone stress); and/or organic pollution (for example by
  • Advantageous properties, obtained especially from treated seeds, are e.g. improved germination and field establishment, better vigor and/or a more homogen field establishment.
  • the above identified indicators for the health condition of a plant may be interdependent and may result from each other. For example, an increased resistance to biotic and/or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Inversely, a more developed root system may result in an increased resistance to biotic and/or abiotic stress.
  • these interdependencies and interactions are neither all known nor fully understood and therefore the different indicators are described separately.
  • the inventive mixtures effectuate an increased yield of a plant or its product.
  • inventive mixtures effectuate an increased vigor of a plant or its product.
  • inventive mixtures effectuate in an increased quality of a plant or its product. In yet another embodiment the inventive mixtures effectuate an increased tolerance and/or resistance of a plant or its product against biotic stress.
  • inventive mixtures effectuate an increased tolerance and/or resistance of a plant or its product against abiotic stress.
  • the inventive mixtures effect an increase in the yield.
  • the inventive mixtures the inventive mix- tures effects an increase in the yield such as the plant weight and/or the plant biomass (e.g. overall fresh weight) and/or the grain yield and/or the number of tillers.
  • the inventive mixtures effect an improvement of the plant vigor.
  • the inventive mixtures effect an increase in the yield.
  • the inventive mixtures effect an in- crease in the yield such as the plant weight and/or the plant biomass (e.g. overall fresh weight) and/or the grain yield and/or the number of tillers.
  • inventive mixtures are employed by treating the plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow with an effective amount of the active compounds.
  • the application can be carried out in the absense of pest pressure and/or both before and after an infection of the materials, plants or plant propagation materials (preferably seeds) by pests.
  • a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 65 BBCH of the treated plant.
  • a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 55 BBCH of the treated plant.
  • a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 37 BBCH of the treated plant.
  • a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 21 BBCH of the treated plant.
  • a mixture comprising compound (I) and (II) for increasing the health of a plant is applied at a growth stage (GS) between GS 13 and GS 37 BBCH of the treated plant.
  • a mixture comprising compound (I) and (II) for increasing the health of a plant is applied at a growth stage (GS) between GS 13 and GS 37 BBCH of the treated plant.
  • the term "growth stage” refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases.
  • the BBCH-scale uses a decimal code system, which is divided into principal and secondary growth stages.
  • the abbreviation BBCH derives from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany) and the chemical industry.
  • the plants and/or plant propagules are treated simultaneously (together or separately) or subsequently with a mixture as described above.
  • Such subsequent application can be carried out with a time interval which allows a combined action of the applied compounds.
  • the time interval for a subsequent application of compound (I) and compound (II) ranges from a few seconds up to 3 months, preferably, from a few seconds up to 1 month, more preferably from a few seconds up to 2 weeks, even more preferably from a few seconds up to 3 days and in particular from 1 second up to 24 hours.
  • the application rates of the mixtures are between 0,3 g/ha and 1500 g/ha, depending on various parameters such as the treated plant species or the mixture applied. In a preferred embodiment of the method according to the invention, the application rates of the mixtures are between 5 g/ha and 750 g/ha. In an even more preferred embodiment of the method according to the invention, the application rates of the mixtures are between 20 g/ha and 500 g/ha, in particular from 20 g/ha to 300 g/ha.
  • amounts of from 0,01 g to 3 kg, in particular amounts from 0,01 g to 1 kg of inventive mixtures are generally required per 100 kg of plant propagation material (preferably seed).
  • amounts of from 0,01 g to 250 g of inventive mixtures are required per 100 kg of plant propagation material (preferably seed).
  • amounts of from 0,01 g to 150 g of inventive mixtures are required per 100 kg of plant.
  • compounds I and II present in the inventive mixtures are used in "effective amounts". This means that they are used in a quantity which allows to obtain the desired effect which is a synergistic increase of the health of a plant but which does not give rise to any phytotoxic symptom on the treated plant.
  • compound (I) and compound (II) are employed in amounts which result in a synergistic effect.
  • the pesticial composition for increasing the health of a plant comprises a liquid or solid carrier and a mixture as described above.
  • the inventive mixtures can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the mixtures accord- ing to the present invention.
  • the formulations are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030,
  • the agrochemical formulations may also comprise auxiliaries which are customary in agrochemical formulations.
  • the auxiliaries used depend on the particular application form and active substance, respectively.
  • suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations).
  • Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. 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 and other solid carriers.
  • mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammonium phosphate, ammoni
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore conden
  • methylcellulose methylcellulose
  • hydrophobically modified starches polyvinyl alcohols (Mowiol® types, Clariant, Swit- zerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvi- nylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.
  • thickeners i.e. compounds that impart a modified flowability to formulations, i.e.
  • Xanthan gum Kel- zan®, CP Kelco, U.S.A.
  • Rhodopol® 23 Rhodia, France
  • Veegum® R.T. Vanderbilt, U.S.A.
  • Attaclay® Engelhard Corp., NJ, USA
  • Bactericides may be added for preservation and stabilization of the formulation.
  • suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).
  • suitable anti- freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • anti-foaming agents are silicone emulsions (such as e.g. Silikon® SRE, Wacker, Ger- many or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • tackifiers or binders examples include polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).
  • Powders, materials for spreading and dusts can be prepared by mixing or concomi- tantly grinding the compounds (I) and/or (ll)and, if appropriate, further active substances, with at least one solid carrier.
  • Granules e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., 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 and other solid carriers.
  • formulation types are:
  • compositions 15 parts by weight of compounds of the inventive mixtures are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil eth- oxylate (in each case 5 parts by weight). Dilution with water gives an emulsion.
  • the composition has an active substance content of 15% by weight.
  • Emulsions (EW, EO, ES)
  • 25 parts by weight of compounds of the inventive mixtures are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil eth- oxylate (in each case 5 parts by weight).
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • the composition has an active substance content of 25% by weight.
  • compositions 50 parts by weight of compounds of the inventive mixtures are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • the composition has an active substance content of 50% by weight.
  • Water-dispersible powders and water-soluble powders 75 parts by weight of compounds of the inventive mixtures are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • the active substance content of the composition is 75% by weight.
  • Dustable powders (DP, DS)
  • the agrochemical formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances.
  • the compounds of the inventive mixtures are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • the compounds of the inventive mixtures can be used as such or in the form of their compositions, e.g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring.
  • the application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the compounds present in the inventive mixtures.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • the substances can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • a wetter, tackifier, dispersant or emulsifier it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of compounds of the inventive mixtures .
  • the compounds of the inventive mixtures may also be used successfully in the ultra- low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
  • UUV ultra- low-volume process
  • Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until
  • compositions of this invention may also contain fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.
  • fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners.
  • the compounds contained in the mixtures as defined above can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • applying the compound (I) and compound (II) is to be understood to denote, that at least the compound (I) and compound (II) occur simultaneously at the site of action (i.e. plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow) in a effective amount.
  • site of action i.e. plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow
  • the compound (I) and compound (II) can be obtained by applying the compound (I) and compound (II) simultaneously, either jointly (e.g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance ap- plied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s).
  • the order of application is not essential for working of the present invention.
  • the weight ratio of the compounds generally depends from the properties of the compounds of the inventive mixtures.
  • the compounds of the inventive mixtures can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
  • kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition.
  • kits may include the compound (I) and compound (II) and/or an adjuvant component and/or a further pesticidal compound (e.g. insecticide, fungicide or herbicide) and/or a growth regulator component).
  • a further pesticidal compound e.g. insecticide, fungicide or herbicide
  • One or more of the components may already be com- bined together or p re-formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister.
  • kits may include one or more separate con- tainers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition.
  • a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane.
  • the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquid or the agrochemical composition according to the invention is thus obtained.
  • 50 to 500 liters of the ready-to-use spray liquid are applied per hectare of agricultural useful area, preferably 50 to 400 liters.
  • compositions such as parts of a kit or parts of the inventive mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
  • either individual compounds of the inventive mixtures formu- lated as composition or partially premixed components e.g. components comprising the compound (I) and compound (II) may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
  • either individual components of the composition according to the invention or partially premixed components e.g. components comprising the compound (I) and compound (II) can be applied jointly (e.g. after tankmix) or consecutively.
  • inventive mixtures are employed by treating the plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow with an effective amount of the active compounds.
  • the application rates of the inventive mixtures are from 0,3 g/ha to 2000 g/ha, preferably 5 g/ha to 2000 g/ha, more preferably from 50 to 900 g/ha, in particular from 50 to 900 g/ha.
  • the application rates are in the range of from 0,1 to 6,0 kg of active ingredient (acid equivalent) per hectare, depending on various parameters such as the weather conditions and the plant species.
  • a variant of the present invention also comprises seed treatment with compound (II) followed by foliar spraying with compound (I).
  • Seed treatment can be made into the seedbox before planting into the field.
  • the weight ratio in the binary or ternary mixtures of the present invention generally depends on the properties of the compounds of the inven- tive mixtures.
  • compositions which are especially useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS)
  • I Dustable powders (DP, DS) These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation material (and also in furrow treatment).
  • the compounds or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the application rates of the inventive mixture are generally for the formulated product (which usually comprises from 10 to 750 g/l of the active(s)).
  • the invention also relates to the propagation products of plants, and especially the seed comprising, that is, coated with and/or containing, a mixture as defined above or a composition containing the mixture of two or more active ingredients or a mixture of two or more compositions each providing one of the active ingredients.
  • the plant propagation material (preferably seed) comprises the inventive mixtures in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material (preferably seed).
  • the separate or joint application of the compounds of the inventive mixtures is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
  • the mixture of the invention is also suitable for combating animal pests, preferably invertebrate pests.
  • invertebrate pest encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
  • Invertebrate pests controlled by the mixture of the invention include for example: Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella,
  • beetles Coldeoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtip
  • dipterans dipterans
  • Aedes aegypti Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycor
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci; hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps,
  • homopterans e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae,
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
  • orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus; Arachnoidea, such as arachnids (Acarina), e.g.
  • Argasidae such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
  • Siphonatera e.g. Xenopsylla cheopsis, Ceratophyllus spp.
  • the mixture of the invention is useful for the control of nematodes, especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species;
  • cyst-forming nematodes Globodera rostochiensis and other Globodera species
  • Het- erodera avenae Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species
  • Seed gall nematodes Anguina species
  • Stem and foliar nematodes Aphelenchoides species
  • Sting nematodes Belonolaimus longicaudatus and other Belonolaimus species
  • Pine nematodes Bursaphelenchus xylophilus and other Bursaphelenchus species
  • Ring nematodes Criconema species, Criconemella species, Criconemoides species, Mesocriconema species
  • Stem and bulb nematodes Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species
  • Awl nematodes Dolichodorus
  • the mixture of the invention is used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina.
  • the mixture of the invention is particularly useful for controlling insects of the order Thysanoptera and Homoptera.
  • the mixtures of the present invention preferably show synergistic action with regard to the pests to be controlled or with regard to the plant-health effects.
  • Synergism can be described as an interaction where the combined effect of a mixture of two or more compounds is greater than the sum of the individual effects of each of the compounds.
  • X and Y are the % control or the % effect observed for the individual compounds at a given concentration.
  • E is the expected combined control/effect, which would be expected in the absence of synergism, if the compounds were applied together at the same concentrations of solo application.
  • the control/effect observed for the mixture i.e. the observed combined control/effect
  • E the expected combined control/effect

Abstract

The present invention, comprising [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3- (cyclopropanecarbonyloxy)-6,12-dihydroxy-4,6a,12b-trimethyl-11 -oxo-9-(pyridin-3-yl)- 1,2,3,4,4a,5,6,6a,12a,12b-decahydro-11 H,12H-benzo[f]pyrano[4,3-b]chromen-4-yl]methyl cydopropanecarboxylate of the formula II and a herbicide, preferably in synergistic effective amounts.

Description

HERBICIDAL MIXTURES
Description
The present invention relates to mixtures comprising, as active compounds
1 ) at least one compound (I) selected from the group consisting of the compounds of following groups b1 ) to b15): b1 ) the group of the lipid biosynthesis inhibitors selected from the group consisting of ACC-herbicides: namely alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclo- fop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P- ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxy- fop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, qui- zalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim and tralkoxydim, and
non ACC herbicides: namely benfuresate, butylate, cycloate, dalapon, dime- piperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate; b2) the group of the ALS inhibitors selected from the group consisting of
sulfonylureas: selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethox- ysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl- sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodo- sulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, metsulfu- ron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfu- ron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazo- sulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron,
imidazolinones: selected from the group consisting of imazamethabenz, ima- zamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and
imazethapyr and their salts and esters,
triazolopyrimidine herbicides and sulfonamides: selected from the group consisting of cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam,
pyrimidinylbenzoates selected from the group consisting of bispyribac, bispyri- bac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithio- bac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2- pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1 -methylethyl ester (CAS 420138-41 -6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]- benzoic acid propyl ester (CAS 420138-40-5) and N-(4-bromophenyl)-2-[(4,6- dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01 -8) and sulfonylaminocarbonyl-triazolinone herbicides selected from the group consisting of flucarbazone, flucarbazone-sodium, propoxycarbazon, propoxycarba- zon- sodium, thiencarbazone and thiencarbazone-methyl;
b3) the group of the photosynthesis inhibitors selected from the group consisting of arnica rbazone,
inhibitors of the photosystem II, selected from the group consisting of triazine herbicides, including chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, des- metryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, propazin, simazin, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin,
aryl urea compounds such as chlorobromuron, chlorotoluron, chloroxuron, dime- furon, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, metha- benzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, te- buthiuron and thiadiazuron,
phenyl carbamates such as desmedipham, karbutilat, phenmedipham and phenmedipham-ethyl,
nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters,
uraciles such as bromacil, lenacil and terbacil,
bentazon, bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-dimetilsulfate;
b4) the group of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, ben- zfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlometh- oxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumi- clorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, flu- thiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluor- fen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, ethyl [3-[2-chloro-4-fluoro-5-(1 -methyl-6- trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2- pyridyloxy]acetate (CAS 353292-31 -6; S-3100), N-ethyl-3-(2,6-dichloro-4- trifluoromethylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452098-92- 9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1 H- pyrazole-1 -carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4- trifluoromethylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452099-05-
7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl- 1 H-pyrazole-1 -carboxamide (CAS 45100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)- 3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4- dione, 1 ,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro- 2H-benzo[b][1 ,4]oxazin-6-yl)-1 ,3,5-triazinane-2,4-dione, 2-(2,2,7-Trifluoro-3-oxo- 4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-
1 .3- dione, and 1 -Methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-
3.4- dihydro-2H-benzo[1 ,4]oxazin-6-yl)-1 H-pyrimidine-2,4-dione;
b5) the group of the bleacher herbicides selected from the group consisting of
PDS inhibitors selected from the group consisting of beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, and 4-(3- trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33- 7),
HPPD inhibitors selected from the group consisting of benzobicyclon, ben- zofenap, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sul- cotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone, and bleacher, unknown target selected from the group consisting of aclonifen, ami- trole, clomazone and flumeturon;
b6) the group of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts;
b7) the group of the glutamine synthase inhibitors selected from the group consisting of bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and ist salts, in particular glufosinate-P or glufosinate-ammonium;
b8) the group of the DHP synthase inhibitors selected from the group consisting of asu- lam; or from
b9) the group of the mitose inhibitors selected from the group consisting of compounds of group K1 selected from the group consisting of dinitroanilines such as benflu- ralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin,
phosphoramidates such as amiprophos, amiprophos-methyl and butamiphos, benzoic acid herbicides such as chlorthal and chlorthal-dimethyl,
pyridines such as dithiopyr and thiazopyr,
benzamides such as propyzamide and tebutam;
and compounds of group K2 selected from the group consisting of chlorpropham, propham and carbetamide, among these, compounds of group K1 , in particular dinitroanilines are preferred;
b10) the group of the VLCFA inhibitors selected from the group consisting of
chloroacetamides such as acetochlor, alachlor, butachlor, dimethachlor, di- methenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethox- amid, pretilachlor, propachlor, propisochlor and thenylchlor,
oxyacetanilides such as flufenacet and mefenacet,
acetanilides such as diphenamid, naproanilide and napropamide,
tetrazolinones such as fentrazamide, and other herbicides such as anilofos, cafenstrole, fenoxasulfone, ipfencarba- zone, piperophos and pyroxasulfone;
he group of the cellulose biosynthesis inhibitors selected from the group consisting of chlorthiamid, dichlobenil, flupoxam, isoxaben, 1 -cyclohexyl-5- pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3-ylamine and piperazine compounds of formula III,
Figure imgf000005_0001
in which
A is phenyl or pyridyl where Ra is attached in the ortho-position to the point of attachment of A to a carbon atom;
Ra is CN, N02, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy Ci-C4-haloalkoxy or D-C(=0)-Ra1 ;
Ry is d-Ce-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, NRARB or Ci-C4-haloalkyl and q is 0, 1 or 2;
RA,RB independently of one another are hydrogen, Ci-C6-alkyl, C3-C6- alkenyl and C3-C6-alkynyl; together with the nitrogen atom to which they are attached, RA, RB may also form a five- or six-membered saturated, partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S, which ring may be substituted by 1 to 3 groups Raa;
D is a covalent bond or Ci-C4-alkylene;
Ra1 is hydrogen, OH, Ci-C8-Alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl;
Raa is halogen, OH, CN, N02, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4- haloalkoxy, S(0)qRy, D-C(=0)-Ra1 and tri-Ci-C4-alkylsilyl;
Rb independently of one another is CN, NO2, halogen, Ci-C4-alkyl, Ci-C4- haloalkyl, C2-C4-alkenyl, C3-C6-alkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, ben-
Figure imgf000005_0002
Rb together with the group Ra or Rb attached to the adjacent ring atom may also form a five- or six-membered saturated or partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S, which ring may be partially or fully substituted by Raa;
p is 0 or1 ;
R30 is hydrogen, Ci-Ci2-alkyl, C3-Ci2-alkenyl, C3-Ci2-alkynyl, Ci-C4-alkoxy or C(=0)R40, which can be partially or fully be substituted by Raa groups; R40 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; where in groups R30, Ra and their sub-substituents the carbon chains and/or the cyclic groups may carry 1 , 2, 3 or 4 substituents Raa and/or Ra1 ;
R31 is Ci-C4-alkyl;
R32 is OH, NH2, Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-haloalkyl or C(=0)R25;
R25 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-halo-alkoxy
R33 is hydrogen, or R33 and R34 together are a covalent bond;
R34, R35, R36, R37 independently of one another are hydrogen;
R38, R39 independently of one another are hydrogen, halogen or OH;
b12) the group of the decoupler herbicides selected from the group consisting of di- noseb, dinoterb and DNOC and its salts;
b13) the group of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, 2,4-DB and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, bena- zolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr and its salts or esters, MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, and aminocyclopyrachlor and its salts and esters;
b14) the group of the auxin transport inhibitors selected from the group consisting of diflufenzopyr and its salts, naptalam and its salts;
b15) the group of the other herbicides selected from the group consisting of bromobu- tide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazo- met, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flam- prop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosa- mine, fosamine-ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl- dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6- methylphenoxy)-4-pyridazinol (CAS 499223-49-3) and its salts and esters; and 2) a compound (II), which is the compound of formula I I
Figure imgf000007_0001
The mixture of the present invention generally includes the at least one compound I and the compound II in synergistically effective amounts.
The mixtures of the present invention will have herbicide action due to the presence of the compound I as well as insecticide, acaricide or nematicide action due to the presence of the compound II. The mixture of the present invention generally leads to a synergism between the at least one compound I and the compound II. Synergism in terms of the present invention means that the use of the inventive mixture leads to an effect which surpasses the additive effect (in mathematical terms) of the compounds I and II, when applied indi- vually. Hence, the term "in synergistically effective amounts" refers to the fact that the purely additive effect (in mathematical terms) of the application of the individual compounds is surpassed by the application of the inventive mixture.
Within the scope of the invention, in particular the health of a plant is increased synergistically. The term "in synergistically effective amounts" refers to the fact that the purely additive effect (in mathematical terms) of the application of the individual compounds is surpassed by the application of the inventive mixture. The synergistic increase of the health of a plant is more than surprising, since it can be assumed that nematicidal compounds and herbicides have completely different mode of actions. The term "effective amount" denotes an amount of the inventive mixtures, which is sufficient for achieving the synergistic plant health effects, in particular the plant health effects as defined herein, especially the yield effects as defined herein. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. Anyway, the skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors, e.g. the treated cultivated plant or material and the climatic conditions. The present invention also relates to a method for increasing the health of a plant, in particular in a synergistic manner, in particular the yield of a plant, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with a effective amount, in particular with a synergistically effective amount, of a mixture as defined above.
The compounds (I) as well as their action and methods for producing them are generally known. For instance, the commercially available compounds can be found in "The Pesticide Manual, 15th Edition, British Crop Protection Council (2009)" among other publications.
The respective compounds I can also be used as in their form as agriculturally acceptable salts and esters.
In the case of salts, suitable salts include those salts, where the counterion is an agri- culturally acceptable cation or anion. Suitable agriculturally acceptable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium substituted ammonium (hereinafter also termed as organoam- monium) in which one to four hydrogen atoms are replaced by Ci-C4-alkyl, hydroxy-Ci- C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, pentylammonium, hexylammonium, heptylammonium, 2- hydroxyethylammonium (olamine salts), 2-(2-hydroxyethoxy)eth-1 -ylammonium (digly- colamine salts), di(2-hydroxyeth-1 -yl)ammonium (diolamine salts), tri(2- hydroxyethyl)ammonium (trolamine salts), tris(3-propanol)amonium, benzyltrimethyl- ammonium, benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium such as trimethylsulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Suitable agriculturally acceptable anions are in particular the halogenides, especially the chlorides, the nitrates, sulfates, hydrogensulfates, phosphates, hydrogenphos- phates, ammoniumhydrogenphosphates, borates including orthoborates and metabo- rates such as diborates and pentaborates, formiates, acetates, propionates etc.
Compounds I having a carboxylic acid group may also be used in the form of their esters. Suitable ester include the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n- pentyl, n-hexyl, isooctyl, 2-methoxylethyl, 2-ethoxyethyl, 1 -methyl-2-butoxyethyl (bu- tometyl), 2-butoxyethyl (butotyl), 3-butoxypropyl, 2-butoxypropyl, 2-ethylhexyl and mexyl (1 -methylhexyl) esters.
For example, suitable salts of dicamba are dicamba-sodium, dicamba-potassium, dicamba-methylammonium, dicamba-dimethylammonium, dicamba- isopropylammonium, dicamba-diglycolamine, dicamba-olamine, dicamba-diolamine and dicamba-trolamine. Examples of a suitable ester are dicamba-methyl and dicamba-butoyl.
Suitable salts of 2,4-D are 2,4-D dimethylammonium, 2,4-D diethanolammonium, 2,4-D triethanolammonium, 2,4-D triisopropanolammonium, 2,4-D sodium; 2,4-D isopropylammonium. Examples of a suitable ester of 2,4-D are 2,4-D-butotyl, 2,4-D-butyl, 2,4- D-ethyl, 2,4-D-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl. Suitable salts of 2,4-DB are for example 2,4-DB sodium, 2,4-DB potassium and 2,4-DB dimethylammonium.
Suitable salts of dichlorprop are for example dichlorprop potassium and dichlorprop dimethylammonium. Examples of a suitable ester of dichlorprop are dichlorprop-butotyl and dichlorprop-isoctyl.
Suitable salts and esters of MCPA include MCPA-butotyl, MCPA-butyl, MCPA- dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-thioethyl, MCPA-2- ethylhexyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA- olamine, MCPA-potassium, MCPA-sodium and MCPA-trolamine. A suitable salt of
MCPB is MCPB sodium. A suitable ester of MCPB is MCPB-ethyl.
Suitable salts of clopyralid are clopyralid potassium, clopyralid olamine and clopyralid triisopropanolammonium.
Examples of a suitable ester of fluroxypyr are fluroxypyr-meptyl and fluroxypyr-2- butoxy-1 -methylethyl, wherein fluroxypyr-meptyl is preferred.
Suitable salts of picloram are picloram dimethylammonium, picloram potassium, piclo- ram triisopropanolammonium, picloram triisopropylammonium and picloram trolamine. A suitable ester of picloram is picloram-isoctyl.
A suitable salt of triclopyr is triclopyr triethalammonium. A suitable ester of triclopyr is triclopyr-butotyl.
Suitable salts and esters of chloramben include chloramben-ammonium, chloramben- diolamine, chloramben-methyl, chloramben-methylammonium and chloramben-sodium. Suitable salts and esters of 2,3,6-TBA include 2,3,6-TBA-dimethylammonium, 2,3,6- TBA-lithium, 2,3,6-TBA-potassium and 2,3,6-TBA-sodium.
Suitable salts and esters of aminopyralid include aminopyralid-potassium and amino- pyralid-tris(2-hydroxypropyl)ammonium.
Suitable salts of glyphosate are for example glyphosate-ammonium, glyphosate- diammonium, glyphoste-dimethylammonium, glyphosate-isopropylammonium, gly- phosate-potassium, glyphosate-sodium, glyphosate-trimesium as well as the etha- nolamine and diethanolamine salts, preferably glyphosate-diammonium, glyphosate- isopropylammonium and glyphosate-trimesium (sulfosate).
Suitable salts of glufosinate are for example glufosinate-ammonium and glufosinate-P. Suitable salts and esters of bromoxynil are for example bromoxynil butyrate, bro- moxynil heptanoate, bromoxynil octanoate, bromoxynil potassium and bromoxynil sodium; Suitable salts of ioxonil are for example ioxonil-octanoate, ioxonil-potassium and ioxo- nil-sodium.
Suitable salts and esters of mecoprop include mecoprop-butotyl, mecoprop- dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-2-ethylhexyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-potassium, mecoprop-sodium and me- coprop-trolamine.
Suitable salts of mecoprop-P are for example butotyl, dimethylammonium, ethylhexyl, potassium and sodium
Suitable salts of diflufenzopyr is diflufenzopyr-sodium.
Suitable salts of naptalam is naptalam -sodium.
Suitable salts of DNOC are for example DNOC-ammonium, DNOC-potassium and DNOC-sodium
Suitable salts and esters of 2,4-DB are for example 2,4-DB-butylester, 2,4-DB- dimethylammonium, 2,4-DB-triisopropanolammonium, 2,4-DB-isoctyl, 2,4-DB- potassium and 2, 4-DB-sodium
Suitable salts of aminocyclopyrachlor are for example aminocyclopyrachlor dimethyl- ammonium, aminocyclopyrachlor triisopropanolammonium, aminocyclopyrachlor sodium and aminocyclopyrachlor potassium The compound II of formula II, which has the IPAC name [(3S,4R,4aR,6S,6aS,12R,
12aS,12bS)-3-(cyclopropanecarbonyloxy)-6, 12-dihydroxy-4,6a,12b-trimethyl-1 1 -oxo-9- (pyridin-3-yl)-1 ,2,3,4,4a,5,6,6a,12a,12b-decahydro-1 1 H,12H-benzo[f]pyrano[4,3- b]chromen-4-yl]methyl cyclopropanecarboxylate (hereinafter referred to as "compound II") as well as its pesticidal action has been described in WO2006/129714 and
WO2009/081851 , insecticidal mixtures thereof in WO2008/108491 and methods for producing the compound are for example disclosed in WO2009/022702.
The piperazine compounds of formula III as defined above (hereinafter referred to as "compound III") as well as its pesticidal action and methods for preparation are de- scribed in WO 2010/049369, WO 2010/037727 und WO 2010/012649.
In crop protection, there is a continuous need for compositions that improve the health of plants. Healthier plants are desirable since they result among others in better yields and/or a better quality of the plants or crops. Healthier plants also better resist to biotic and/or abiotic stress. A high resistance against biotic stresses in turn allows the person skilled in the art to reduce the quantity of pesticides applied and consequently to slow down the development of resistances against the respective pesticides.
It is therefore an object of the present invention to provide a pesticidal composition which solves the problems outlined above, and which should, in particular, improve the health of plants, in particular the yield of plants. We have found that these objects are in part or in whole achieved by using the mixtures as defined in the outset.
Preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b1 ) the group of the lipid biosynthesis inhibitors, wherein in this group, preference is given to compounds selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P- butyl, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalo- fop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim and tralkoxydim, benfure- sate, dimepiperate, EPTC, esprocarb, ethofumesate, molinate, orbencarb, prosulfo- carb, thiobencarb and triallate.
Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors, wherein in this group, preference is given to the compounds selected from the group consisting of
sulfonylureas, in particular those selected from the group consisting of amidosul- furon, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cyclo- sulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfu- ron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazosul- furon, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfosulfu- ron, thifensulfuron-methyl, triasulfuron, trifloxysulfuron, triflusulfuron and tritosul- furon.
Preferred mixtures of the invention are also mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors, selected from the group consisting of
the imidazolinones selected from the group consisting of imazamethabenz, ima- zamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and
imazethapyrand their salts.
Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors, selected from the group consisting of
the triazolopyrimidine herbicides and sulfonamides selected from the group con- sisting of diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam and Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from b2) the group of the ALS inhibitors selected from the group consisting of
the pyrimidinylbenzoates selected from the group consisting of bispyribac- sodium, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, flucar- bazone-sodium, propoxycarbazon- sodium and thiencarbazone-methyl.
Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein compound (I) is selected from the group b3), i.e. the group of the photosynthesis inhibitors (group b4), wherein in this group, preference is given to the compounds selected from the group consisting of amicarbazone, ametryn, atrazine, chloridazone, cyanazine, hexazinone, metribuzin, simazin, terbuthy- lazin and terbutryn, and wherein in this group is likewise preference is given to the compounds selected from the group consisting of the aryl ureas such as chlorotoluron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron and thiadiazuron, the phenyl carbamates desmedipham, karbutilat or phenmedipham, bromoxynil and its salts and esters, bentazon and bentazon-sodium, pyridate, propanil, diquat, paraquat, paraquat-dichloride. Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the protoporphyrinogen-IX oxidase inhibitors (group b4), wherein in this group, preference is given acifluorfen, acifluorfen-sodium, bencarbazone, ben- zfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, cinidon-ethyl, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fomesafen, lacto- fen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraflufen-ethyl, saflufenacil, sulfentrazone, ethyl [3-[2-chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo- 1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31 -6; S- 3100), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl]-1 ,5- dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4-dione, 1 ,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3- oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1 ,4]oxazin-6-yl)-1 ,3,5-triazinane-2,4- dione, 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)- 4,5,6,7-tetrahydro-isoindole-1 ,3-dione, and 1 -methyl-6-trifluoromethyl-3-(2,2,7-trifluoro- 3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-1 H-pyrimidine-2,4-dione.
Preferred mixturesof the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the bleacher herbicides (group b5), wherein in this group, preference is given to the PDS inhibitors diflufenican, flurochloridone and picolinafen, to the HPPD inhibi- tors benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone and to the bleachers aclonifen, amitrole, clomazone and flumeturon. Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein compound (I) is selected from the group b6), i.e. the group of the EPSP synthase inhibitors, wherein in this group, preference is given to glyphosate and its salts.
Preferred mixtures are mixtures comprising compound I and compound II, wherein compound (I) is selected from b7) the group of the glutamine synthase inhibitors, wherein in this group, preference is given to glufosinate, and its salts. Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b9), i.e. the group of the mitose inhibitors, wherein in this group, preference is given to thedinitroanilines, in particular benfluralin, ethalfluralin, oryzalin, pendi- methalin and trifluralin, and the pyridines, in particular dithiopyr and thiazopyr.
Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10), i.e. the group of the VLCFA inhibitors, wherein in this group, preference is given to the chloroacetamides, which are in particular selected from the group con- sisting of acetochlor, alachlor, butachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pretilachlor and thenylchlor, to the the oxyacetanilides which are in particular selected from the group consisting of flufenacet and mefenacet, to the tetrazolinone fentrazamide, and to the compounds selected from the group consisting of cafenstrole, fenoxasulfone, ipfencarbazone andpyroxasulfone.
Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b1 1 ), i.e. the group of the cellulose biosynthesis inhibitors, wherein in this group, preference is given to isoxaben and 1 -cyclohexyl-5-pentafluorphenyloxy-14- [1 ,2,4,6]thiatriazin-3-ylamine.
Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the compounds of the general formula III.
Preferred mixtures of the invention are also mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b13), i.e. the group of the auxin herbicides, wherein in this group, preference is given to 2,4-D and its salts and esters, aminopyralid, clopyralid and its salts and es- ters, dicamba and its salts and esters, fluroxypyr and its salts or esters, MCPA and its salts and esters, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, triclopyr and its salts and esters and aminocyclopyrachlor and its salts and esters.
Preferred mixtures of the invention are also mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from the group b14), i.e. the group of the auxin transport inhibitors, wherein in this group, preference is given to diflufenzopyr, and its salts.
Preferred mixtures of the invention are also mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from group b15), wherein in this group, preference is given to cinmethylin, dymron, indano- fan, indaziflam, oxaziclomefone and triaziflam.
More preferred mixtures of the invention are mixtures comprising at least one com- pound I and the compound II, wherein the at least one compound (I) is selected from the group b1 ), i.e. the group of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, fenoxaprop- P-ethyl, fluazifop-P-butyl, haloxyfop-P-methyl, pinoxaden, profoxydim, sethoxydim, te- praloxydim and tralkoxydim, esprocarb, prosulfocarb, thiobencarb and triallate.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b2), i.e. the group of the ALS inhibitors, where the the ALS inhibitors are selected from the group consisting of the sulfonylureas bensulfuron-methyl, chlori- muron-ethyl, cyclosulfamuron, flupyrsulfuron-methyl-sodium, foramsulfuron, iodosulfu- ron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, nicosulfuron, pyrazo- sulfuron-ethyl, rimsulfuron, sulfosulfuron, and tritosulfuron,
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b2), i.e. the group of the ALS inhibitors, where the the ALS inhibitors are selected from the group of the imidazolinones imazamethabenz, imazamethabenz- methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr and their salts. Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b2), i.e. the group of the ALS inhibitors, where the the ALS inhibitors are selected from the group of the triazolopyrimidine herbicides and sulfonamides, which are selected from the group consisting of diclosulam, flumetsulam, florasulam, penox- sulam and pyroxsulam. Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b2), i.e. the group of the ALS inhibitors, where the the ALS inhibitors are selected from the group of the pyrimidinylbenzoates bispyribac-sodium, pyribenzoxim, pyriftalid, propoxycarbazon- sodium and thiencarbazone-methyl.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from group b3), i.e. the group of the photosynthesis inhibitors selected from the group consisting of ametryn, atrazine, cyanazine, hexazinone, metribuzin, simazin, terbuthy- lazin and terbutryn.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the b4) protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, acifluorfen-sodium, flumioxazin, fomesafen, lactofen, oxyfluorfen, saflufenacil, sulfentrazone, ethyl [3-[2-chloro-4-fluoro-5-(1 -methyl-6- trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2- pyridyloxy]acetate, 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H- benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1 ,3-dione and 1 -methyl-6-trifluoro- methyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-1 H- pyrimidine-2,4-dione.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the b5) bleacher herbicides, which are selected from the group consisting of diflufenican, flurochloridone and picolinafen,
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the b5) bleacher herbicides, which are selected from the group of the HPPD inhibitors: benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone. Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the b5) bleacher herbicides, which are selected from the group bleachers amitrole and clomazone.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b6) of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b7) of the glutamine synthase inhibitors selected from the group consisting of glufosinate and its salts.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b9) of the mitose inhibitors selected from the group consisting of the dinitroanilines, in particular from the group consisting of pendimethalin and trifluralin.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10) of the VLCFA inhibitors consisting of the chloroacetamides ace- tochlor, dimethenamid-P, metazachlor, metolachlor, metolachlor-S and pretilachlor and the oxyacetanilides flufenacet and mefenacet and the tetrazolinone fentrazamide. Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b 1 1 ) of the cellulose biosynthesis inhibitors selected from the group consisting of isoxaben and 1 -cyclohexyl-5-pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3- ylamine.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b 1 1 ) of the cellulose biosynthesis inhibitors selected from the group of the compounds of the formula III.
Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b13) of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, aminopyralid and its salts, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr-meptyl, MCPA, MCPB and its salts and esters, mecoprop and its salts and esters, quinclorac and quinmerac.
Also more preferred mixtures of the invention are mixtures comprising a compound I and the compound II, wherein the compound (I) is the b14) the auxin transport inhibitor diflufenzopyr. Also more preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from group b15) consisting of cinmethylin, dymron, indanofan, indaziflam, oxaziclome- fone and triaziflam.
Most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b1 ) of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, pinoxaden, profoxydim, sethoxydim, te- praloxydim and tralkoxydim.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the ALS inhibitors b2) selected from the group consisting of the sul- fonylureas chlorimuron-ethyl, foramsulfuron, nicosulfuron, rimsulfuron and tritosulfuron,
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the ALS inhibitors b2) selected from the group consisting of the imi- dazolinones imazamox, imazapic, imazapyr, imazaquin and imazethapyr and their salts.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group of the ALS inhibitors b2) selected from the group consisting of the pyrimidinylbenzoates pyribenzoxim and pyriftalid.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b3) of the photosynthesis inhibitors selected from the group consisting of ametryn, atrazine, cyanazine, simazin and terbuthylazin.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b4) of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, flumioxazin, fomesafen, saflufenacil and sulfentrazone.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b5) of the bleacher herbicides, selected from the group consisting of the PDS diflufenican, flurochloridone and picolinafen, Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b5) of the bleacher herbicides, selected from the group consisting ofthe HPPD inhibitors: benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tembotrione and topramezone.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the bleacher clomazone.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b6) of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is the the mi- tose inhibitor pendimethalin. Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10) of the VLCFA inhibitors selected from the group consisting of the chloroacetamides acetochlor, dimethenamid-P, metazachlor, metolachlor, metolachlor- S and pretilachlor.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b10) of the VLCFA inhibitors selected from the group consisting of the oxyacetanilide flufenacet and the tetrazolinone fentrazamide.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is selected from the group b13) of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, clopyralid and its salts and esters, dicamba and its salts and esters, MCPA, quinclorac and quinmerac.
Also most preferred mixtures of the invention are mixtures comprising at least one compound I and the compound II, wherein the at least one compound (I) is indaziflam.
Utmost preference is given to the following mixtures: M-1 (compound II and clethodim); M-2 (compound II and clodinafop-propargyl); M-3 (compound II and cycloxydim ); M-4 (compound II and pinoxaden); M-5 (compound II and nicosulfuron); M-6 (compound II and tritosulfuron); M-7 (compound II and ima- zamox); M-8 (compound II and imazapic); M-9 (compound II and imazaquin ); M-10 (compound II and imazethapyr); M-1 1 (compound II and pyribenzoxim ); M-12 (compound II and pyriftalid ); M-13 (compound II and atrazine); M-14 (compound II and si- mazin); M-15 (compound II and terbuthylazin); M-16 (compound II and diuron); M-17 (compound II and isoproturon); M-18 (compound II and bromoxynil); M-19 (compound II and bentazon); M-20 (compound II and acifluorfen); M-21 (compound II and fome- safen); M-22 (compound II and saflufenacil); M-23 (compound II and picolinafen); M-24 (compound II and mesotrione); M-25 (compound II and sulcotrione); M-26 (compound II and tembotrione); M-27 (compound II and topramezone ); M-28 (compound II and clo- mazone); M-29 (compound II and glyphosate); M-30 (compound II and glyphosate- isopropylammonium ); M-31 (compound II and glyphosate-trimesium (sulfosate)); M-32 (compound II and glyphosate-diammonium); M-33 (compound II and pendimethalin); M-34 (compound II and acetochlor); M-35 (compound II and dimethenamid-P); M-36 (compound II and metazachlor ); M-37 (compound II and flufenacet); M-38 (compound II and 2, 4-D and its salts and esters); M-39 (compound II and dicamba and its salts and esters); M-40 (compound II and MCPA); M-41 (compound II and quinclorac) and M-42 (compound II and indaziflam).
The ratios by weight for the respective mixtures, in particular the binary mixtures, comprising the at least one compound I and the compound II are from from 1 :200 to 200:1 , in particular from 1 :100 to 100:1 or from 1 :50 to 50:1 , wherein the weight ratio of com- pound I is calculated as the free acid.
The mixtures of the invention may be binary mixtures comprising one compound I and the compound II. The mixtures of the invention may also be mixtures comprising more than one compound I, e.g. 2, 3 or 4 compounds I, and the compound II.
All embodiments of the mixtures set forth above (including the respective preferences as set forth above) are hereinbelow referred to as "inventive mixture".
The inventive mixtures can further contain one or more insecticides, fungicides, herbi- cides and plant growth regulators.
The present invention relates to a method for increasing the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with an effective amount of an inven- tive mixture. Preferably, the present invention relates to a method for increasing the yield of a plant, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with an effective amount of an inventive mixture.
In a more preferred embodiment, the present invention relates to a method of increasing the health of a plant by treating plants, parts of such plants or at their locus of growth with an effective amount of inventive mixture. In a further more preferred embodiment, the present invention relates to a method of increasing the yield of a plant by treating plants, parts of such plants or at their locus of growth with an effective amount of inventive mixture.
The compounds contained in the mixtures as defined above can be applied simultane- ously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
According to this invention, applying the compound I and compound II is to be understood to denote, that at least the compound I and compound II occur simultaneously at the site of action (i.e. plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow) in an effective amount.
This can be obtained by applying the compound I and compound II simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
In the inventive mixtures, the weight ratio of the compounds generally depends from the properties of the compounds of the inventive mixtures.
The compounds of the inventive mixtures can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition. E. g., kits may include the compound I and compound II and/or an adjuvant component and/or a further pesticidal compound (e.g. insecticide, fungicide or herbicide) and/or a growth regulator component). One or more of the components may already be combined together or p re-formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or can- ister. In other embodiments, two or more components of a kit may be packaged separately, i. e., not p re-formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquid or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready-to-use spray liquid are applied per hectare of agricultural useful area, preferably 50 to 400 liters.
According to one embodiment, individual compounds of the inventive mixtures formulated as composition (or formulation) such as parts of a kit or parts of the inventive mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
In a further embodiment, either individual compounds of the inventive mixtures formulated as composition or partially premixed components, e.g. components comprising the compound I and compound II may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising the compound I and compound II , can be applied jointly (e. .g. after tankmix) or consecutively. In a preferred embodiment, the term yield refers to fruits in the proper sense, vegetables, nuts, grains and seeds.
The term "plants" generally comprises all plants of economic importance and/or men- grown plants. They are preferably selected from agricultural, silvicultural and ornamen- tal plants, more preferably agricultural plants and silvicultural plants, utmost preferably agricultural plants. The term "plant (or plants)" is a synonym of the term "crop" which is to be understood as a plant of economic importance and/or a men-grown plant. The term "plant" as used herein includes all parts of a plant such as germinating seeds, emerging seedlings, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions. The plants to be treated according to the invention are selected from the group consisting of agricultural, silvicultural, ornamental and horticultural plants more preferably from agricultural plants.
In one embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term "horticultural plants" are to be understood as plants which are commonly used in horticulture - e.g. the cultivation of ornamentals and/or fruits. Examples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
In one embodiment, the plant to be treated according to the method of the invention is an ornamental plant. Ornamental plants" are plants which are commonly used in gar- dening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
In one embodiment, the plant to be treated according to the method of the invention is a silvicultural plants. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm and oak.
In one embodiment, the plant to be treated according to the method of the invention is an agricultural plant. Agricultural plants are plants of which a part or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Agricultural plants also include the horticultural plants fruits and vegetables. Thus, the term agricultural plants include cereals, e.g. wheat, rye, barley, triticale, oats, sorghum or rice; beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, juncea (Brassica juncea), linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as cucumbers, spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e.g. conifers.
In a preferred emobodiment, the plants to be treated in accordance with the method of the present invention are agricultural plants. All of the above-mentioned plants may be also modified plants, which have been modified by breeding, mutagenesis or genetic engineering (transgenic and non-transgenic plants). Genetically modified plants are plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that it cannot readily be obtained by cross breeding under natural circumstances, mutations or natural recombina- tion.
Plants as well as the propagation material of said plants, which can be treated with the inventive mixtures include all modified non-transgenic plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures. For example, mixtures according to the present invention can be applied (as seed treatment, foliar spray treatment, in-furrow application or by any other means) also to plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agri_products.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s), oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated or farnesy- lated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e.g. have been rendered tolerant to applications of specific classes of herbicides. Tolerance to herbicides can be obtained by creating insensitivity at the site of action of the herbi- cide by expression of a target enzyme which is resistant to herbicide; rapid metabolism (conjugation or degradation) of the herbicide by expression of enzymes which inactivate herbicide; or poor uptake and translocation of the herbicide. Examples are the expression of enzymes which are tolerant to the herbicide in comparison to wild type enzymes, such as the expression of 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS), which is tolerant to glyphosate (see e.g. Heck et.al, Crop Sci. 45, 2005, 329- 339; Funke et al., PNAS 103, 2006, 13010-13015; US5188642, US4940835, US5633435, US5804425, US5627061 ), the expression of glutamine synthase which is tolerant to glufosinate and bialaphos (see e.g. US5646024, US5561236) and DNA constructs coding for dicamba-degrading enzymes (see e.g. for general reference US 2009/0105077, and e.g. US7105724 for dicamba resistaince in bean, maize (for maize see also WO2008051633), cotton (for cotton see also US5670454), pea, potatoe, sorghum, soybean (for soybean see also US5670454), sunflower, tobacco, tomato (for tomato see also US5670454)). Gene constructs can be obtained, for example, from micro-organism or plants, which are tolerant to said herbicides, such as the Agrobacte- rium strain CP4 EPSPS which is resistant to glyphosate; Streptomyces bacteria which are resistance to glufosinate; Arabidopsis, Daucus carota, Pseudomonoas ssp. or Zea mays with chimeric gene sequences coging for HDDP (see e.g. W01996/38567, WO 2004/55191 ); Arabidopsis thaliana which is resistant to protox inhibitors (see e.g. US2002/0073443).
Examples of commercial available plants with tolerance to herbicides, are the corn varieties "Roundup Ready® Corn", "Roundup Ready 2®" (Monsanto), "Agrisure GT®", "Agrisure GT/CB/LL®", "Agrisure GT/RW®",„Agrisure 3000GT® " (Syngenta),
"YieldGard VT Rootworm/RR2®" and "YieldGard VT Triple®" (Monsanto) with toler- ance to glyphosate; the corn varieties "Liberty Link®" (Bayer), "Herculex I®", "Herculex RW®", "Herculex® Xtra"(Dow, Pioneer), "Agrisure GT/CB/LL®" and "Agrisure
CB/LL/RW®" (Syngenta) with tolerance to glufosinate; the soybean varieties "Roundup Ready® Soybean" (Monsanto) and "Optimum GAT®" (DuPont, Pioneer) with tolerance to glyphosate; the cotton varieties "Roundup Ready® Cotton" and "Roundup Ready Flex®" (Monsanto) with tolerance to glyphosate; the cotton variety "FiberMax Liberty Link®" (Bayer) with tolerance to glufosinate; the cotton variety "BXN®" (Calgene) with tolerance to bromoxynil; the canola varieties ..Navigator® " und ..Compass® " (Rhone- Poulenc) with bromoxynil tolerance; the canola varierty"Roundup Ready® Canola" (Monsanto) with glyphosate tolerance; the canola variety "InVigor®" (Bayer) with glu- fosinate tolerance; the rice variety "Liberty Link® Rice" (Bayer) with glulfosinate tolerance and the alfalfa variety "Roundup Ready Alfalfa" with glyphosate tolerance. Further modified plants with herbicide are commonly known, for instance alfalfa, apple, euca- lyptus, flax, grape, lentils, oil seed rape, peas, potato, rice, sugar beet, sunflower, tobacco, tomatom turf grass and wheat with tolerance to glyphosate (see e.g. US 5188642, US 4940835, US 5633435, US 5804425, US 5627061 ); beans, soybean, cotton, peas, potato, sunflower, tomato, tobacco, corn, sorghum and sugarcane with tolerance to dicamba (see e.g. US 2009/0105077, US 7105724 and US 5670454); pepper, apple, tomato, hirse, sunflower, tobacco, potato, corn, cucumber, wheat, soybean and sorghum with tolerance to 2,4-D (see e.g. US 6153401 , US 6100446, WO 05/107437, US 5608147 and US 5670454); sugarbeet, potato, tomato and tobacco with tolerance to gluphosinate (see e.g. US 5646024, US 5561236); canola, barley, cotton, juncea, lettuce, lentils, melon, millet, oats, oilseed rapre, potato, rice, rye, sorghum, soybean, sugarbeet, sunflower, tobacco, tomato and wheat with tolerance to acetolactate synthase (ALS) inhibiting herbicides, such as triazolopyrimidine sulfonamides, growth inhibitors and imidazolinones (see e.g. US 5013659, WO 06/060634, US 4761373, US 5304732, US 621 1438, US 621 1439 and US 6222100); cereal, sugar cane, rice, corn, tobacco, soybean, cotton, rapeseed, sugar beet and potato with tolerance to HPPD inhibitor herbicides (see e.g. WO 04/055191 , WO 96/38567, WO 97/049816 and US 6791014); wheat, soybean, cotton, sugar beet, rape, rice, corn, sorghum and sugar cane with tolerance to protoporphyrinogen oxidase (PPO) inhibitor herbicides (see e.g. US2002/0073443, US 20080052798, Pest Management Science, 61 , 2005, 277-285). The methods of producing such herbicide resistant plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Further examples of commercial available modified plants with tolerance to herbicides "CLEARFIELD® Corn", "CLEARFIELD® Canola", "CLEARFIELD® Rice", "CLEARFIELD® Lentils", "CLEARFIELD® Sunlowers" (BASF) with tolerance to the imidazolinone herbicides.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ- endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e.g. Photorhabdus spp. or Xenorhab- dus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants capa- ble of synthesizing such toxins are disclosed, e.g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Her- culex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphi- nothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard® I (cotton cultivars producing the Cry1 Ac toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt- Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e.g. EP-A 392225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e.g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e.g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e.g. potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).
Preferred modified plants suitable to be used in the methods of the present invention are those, which are rendered tolerant to the herbicide, which is compound II (includ- ing, but not limited to the above-referred plants) in accordance with the preferences within the inventive mixtures as set forth above. Thus, preferred plants are those, which are resistant to glyphosate, glyphosinate, dicamba and imidazolinones.
Preferred agricultural plants are field crops, sugar beets, cereals such as wheat, rye, barley, triticale, oats, sorghum, rice, corn, cotton, rape, sunflowers, oilseed rape, juncea and canola, vine, legumes such as soybeans, peas and beans (fieldbeans), lentil, sugar cane, turf; ornamentals; vegetables, such as vegetables, such as cucumbers, leeks, paprika spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits (squashes, cucumber or melons ); alfalfa, clover and fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries and citrus fruit, such as oranges, lemons, grapefruits or mandarins; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, juncea (Brassica juncea), linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; fiber plants, such as cotton, flax, hemp or jute;
More preferred agricultural plants are selected from soybean, wheat, sunflower, canola, oilseed rape, corn, cotton, sugar cane, juncea, peas, lentils, alfalfa, vine, and fruits (as defined above) and vegetables as defined above). Most preferred agricultural plants are selected from wheat, barley, corn, soybean, rice, canola, sunflower and fruits (as defined above) and vegetables as defined above). The utmost preferred plants are soybean, vine, and fruits (as defined above) and vegetables as defined above). The term "locus" is to be understood as any type of environment, soil, area or material where the plant is growing or intended to grow as well as the environmental conditions (such as temperature, water availability, radiation) that have an influence on the growth and development of the plant and/or its propagules.
In the terms of the present invention "mixture" means a combination of at least two active ingredients (compounds). In the present case, a mixture used for increasing the health of a plant comprises one compound (I) and one compound (II) or one compound (I) and one compound (II).
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This in- eludes seeds, grains, roots, fruits, tubers, bulbs, rhizomes, cuttings, spores, offshoots, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil, meristem tissues, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained.
The term "propagules" or "plant propagules" is to be understood to denote any structure with the capacity to give rise to a new plant, e.g. a seed, a spore, or a part of the vegetative body capable of independent growth if detached from the parent. In a preferred embodiment, the term "propagules" or "plant propagules" denotes for seed.
The term "synergistically" means that the purely additive increasing effects of a simultaneous, that is joint or separate application of one compound (I) and one compound (II), or the successive application of one compound (I) and one compound (II), is surpassed by the application of an inventive mixture.
The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as increased yield, plant vigor, quality and tolerance to abiotic and/or biotic stress. It has to be emphasized that the above mentioned effects of the inventive mixtures, i.e. enhanced health of the plant, are also present when the plant is not under biotic stress and in particular when the plant is not under pest pressure. It is evident that a plant suffering from fungal or insecticidal attack produces a smaller biomass and leads to a reduced yield as compared to a plant which has been subjected to curative or preven- tive treatment against the pathogenic fungus or any other relevant pest and which can grow without the damage caused by the biotic stress factor. However, the methods according to the invention lead to an enhanced plant health even in the absence of any biotic stress. This means that the positive effects of the mixtures of the invention cannot be explained just by the fungicidal and/or herbicidal activities of the compounds (I) and (II), but are based on further activity profiles. Accordingly, the application of the inventive mixtures can also be carried out in the absence of pest pressure.
Each listed plant health indicator listed below, and which is selected from the groups consisting of yield, plant vigor, quality and tolerance to abiotic and/or biotic stress, is to be understood as a preferred embodiment of the present invention either each on its own or preferably in combination with each other.
According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the inventive mixture.
Increased yield can be characterized, among others, by the following improved properties of the plant: increased plant weight; and/or increased plant height; and/or increased biomass such as higher overall fresh weight (FW); and/or increased number of flowers per plant; and/or higher grain and/or fruit yield ; and/or more tillers or side shoots (branches); and/or larger leaves; and/or increased shoot growth; and/or increased protein content; and/or increased oil content; and/or increased starch content; and/or increased pigment content; and/or increased chlorophyll content (chlorophyll content has a positive correlation with the plant's photosynthesis rate and accordingly, the higher the chlorophyll content the higher the yield of a plant)
"Grain" and "fruit" are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant.
According to the present invention, the yield is increased by at least 4 %, preferable by 5 to 10 %, more preferable by 10 to 20 %, or even 20 to 30 %. In general, the yield increase may even be higher.
Another indicator for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects such as the general visual appearance.
Improved plant vigor can be characterized, among others, by the following improved properties of the plant: improved vitality of the plant; and/or improved plant growth; and/or improved plant development; and/or improved visual appearance; and/or improved plant stand (less plant verse/lodging); and/or improved emergence; and/or en- hanced root growth and/or more developed root system; and/or enhanced nodulation, in particular rhizobial nodulation; and/or bigger leaf blade; and/or bigger size; and/or increased plant height; and/or increased tiller number; and/or increased number of side shoots; and/or increased number of flowers per plant; and/or increased shoot growth; and/or enhanced photosynthetic activity (e.g. based on increased stomatal conductance and/or increased CO2 assimilation rate) ; and/or enhanced pigment content-; and/or earlier flowering; and/or earlier fruiting; and/or earlier and improved germination; and/or earlier grain maturity; and/or less non-productive tillers; and/or less dead basal leaves; and/or less input needed (such as fertilizers or water); and/or greener leaves; and/or complete maturation under shortened vegetation periods; and/or less seeds needed; and/or easier harvesting; and/or faster and more uniform ripening; and/or longer shelf-life; and/or longer panicles; and/or delay of senescence ; and/or stronger and/or more productive tillers; and/or better extractability of ingredients; and/or improved quality of seeds (for being seeded in the following seasons for seed produc- tion); and/or reduced production of ethylene and/or the inhibition of its reception by the plant.
Another indicator for the condition of the plant is the "quality" of a plant and/or its products. According to the present invention, enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the mixtures of the present invention. Enhanced quality can be characterized, among others, by following improved properties of the plant or its product: increased nutrient content; and/or in- creased protein content; and/or increased content of fatty acids; and/or increased metabolite content; and/or increased carotenoid content; and/or increased sugar content; and/or increased amount of essential amino acids; and/or improved nutrient composition; and/or improved protein composition; and/or improved composition of fatty acids; and/or improved metabolite composition; and/or improved carotenoid composition; and/or improved sugar composition; and/or improved amino acids composition ; and/or improved or optimal fruit color; and/or improved leaf color; and/or higher storage capacity; and/or higher processability of the harvested products.
Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors. Biotic and abiotic stress, especially over longer terms, can have harmful effects on plants. Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes. According to the present invention, "enhanced tolerance or resistance to biotic and/or abiotic stress factors" means (1 .) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with an inventive mixture and (2.) that the negative effects are not diminished by a direct action of the inventive mixture on the stress factors, e.g. by its fungicidal or insecticidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive reactions against said stress factors. Negative factors caused by biotic stress such as pathogens and pests are widely known and range from dotted leaves to total destruction of the plant. Biotic stress can be caused by living organisms, such as competing plants (for example weeds), microorganisms (such as phythopathogenic fungi and/or bacteria) and/or viruses. Negative factors caused by abiotic stress are also well-known and can often be observed as reduced plant vigor (see above), for example: dotted leaves, "burned leaves", reduced growth, less flowers, less biomass, less crop yields, reduced nutritional value of the crops, later crop maturity, to give just a few examples. Abiotic stress can be caused for example by: extremes in temperature such as heat or cold (heat stress / cold stress); and/or strong variations in temperature; and/or temperatures unusual for the specific season; and/or drought (drought stress); and/or extreme wetness; and/or high salinity (salt stress); and/or radiation (for example by increased UV radiation due to the decreasing ozone layer); and/or increased ozone levels (ozone stress); and/or organic pollution (for example by phythotoxic amounts of pesticides); and/or inorganic pollution (for example by heavy metal contaminants).
As a result of biotic and/or abiotic stress factors, the quantity and the quality of the stressed plants, their crops and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds. Synthesis, accumulation and storage of proteins are mostly affected by temperature; growth is slowed by almost all types of stress; polysaccharide synthesis, both structural and storage is reduced or modified: these effects result in a decrease in biomass (yield) and in changes in the nutritional value of the product.
Advantageous properties, obtained especially from treated seeds, are e.g. improved germination and field establishment, better vigor and/or a more homogen field establishment. As pointed out above, the above identified indicators for the health condition of a plant may be interdependent and may result from each other. For example, an increased resistance to biotic and/or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Inversely, a more developed root system may result in an increased resistance to biotic and/or abiotic stress. However, these interdependencies and interactions are neither all known nor fully understood and therefore the different indicators are described separately. In one embodiment the inventive mixtures effectuate an increased yield of a plant or its product.
In another embodiment the inventive mixtures effectuate an increased vigor of a plant or its product.
In another embodiment the inventive mixtures effectuate in an increased quality of a plant or its product. In yet another embodiment the inventive mixtures effectuate an increased tolerance and/or resistance of a plant or its product against biotic stress.
In yet another embodiment the inventive mixtures effectuate an increased tolerance and/or resistance of a plant or its product against abiotic stress.
In a preferred embodiment of the invention, the inventive mixtures effect an increase in the yield.
In a preferred embodiment of the invention, the inventive mixtures the inventive mix- tures effects an increase in the yield such as the plant weight and/or the plant biomass (e.g. overall fresh weight) and/or the grain yield and/or the number of tillers.
In another preferred embodiment of the invention, the inventive mixtures effect an improvement of the plant vigor.
In a more preferred embodiment of the invention, the inventive mixtures effect an increase in the yield.
In a most preferred embodiment of the invention, the inventive mixtures effect an in- crease in the yield such as the plant weight and/or the plant biomass (e.g. overall fresh weight) and/or the grain yield and/or the number of tillers.
The inventive mixtures are employed by treating the plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow with an effective amount of the active compounds. The application can be carried out in the absense of pest pressure and/or both before and after an infection of the materials, plants or plant propagation materials (preferably seeds) by pests.
In one embodiment of the invention, a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 65 BBCH of the treated plant. In a preferred embodiment of the invention, a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 55 BBCH of the treated plant. In an even more preferred embodiment of the invention, a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 37 BBCH of the treated plant.
In a most preferred embodiment of the invention, a mixture for increasing the health of a plant is applied at a growth stage (GS) between GS 00 and GS 21 BBCH of the treated plant.
In a preferred embodiment of the invention, a mixture comprising compound (I) and (II) for increasing the health of a plant is applied at a growth stage (GS) between GS 13 and GS 37 BBCH of the treated plant.
In another preferred embodiment of the invention, a mixture comprising compound (I) and (II) for increasing the health of a plant is applied at a growth stage (GS) between GS 13 and GS 37 BBCH of the treated plant.
The term "growth stage" refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases. The BBCH-scale uses a decimal code system, which is divided into principal and secondary growth stages. The abbreviation BBCH derives from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany) and the chemical industry. In one embodiment of the method according to the invention, the plants and/or plant propagules are treated simultaneously (together or separately) or subsequently with a mixture as described above. Such subsequent application can be carried out with a time interval which allows a combined action of the applied compounds. Preferably, the time interval for a subsequent application of compound (I) and compound (II) ranges from a few seconds up to 3 months, preferably, from a few seconds up to 1 month, more preferably from a few seconds up to 2 weeks, even more preferably from a few seconds up to 3 days and in particular from 1 second up to 24 hours.
Herein, we have found that simultaneous, that is joint or separate, application of a compound (I) and a compound (II) or the successive application of a compound (I) and a compound (II) allows an enhanced increase of the health of a plant compared to the control rates that are possible with the individual compounds (synergistic mixtures). In another embodiment of the invention, the mixture as described above is repeatedly applied. If this is the case, the application is repeated two to five times, preferably two times.
When used for increasing the health of a plant, the application rates of the mixtures are between 0,3 g/ha and 1500 g/ha, depending on various parameters such as the treated plant species or the mixture applied. In a preferred embodiment of the method according to the invention, the application rates of the mixtures are between 5 g/ha and 750 g/ha. In an even more preferred embodiment of the method according to the invention, the application rates of the mixtures are between 20 g/ha and 500 g/ha, in particular from 20 g/ha to 300 g/ha.
In the treatment of plant propagation material (preferably seed), amounts of from 0,01 g to 3 kg, in particular amounts from 0,01 g to 1 kg of inventive mixtures are generally required per 100 kg of plant propagation material (preferably seed). In a preferred embodiment of the method according to the invention, amounts of from 0,01 g to 250 g of inventive mixtures are required per 100 kg of plant propagation material (preferably seed). In another preferred embodiment of the method according to the invention, amounts of from 0,01 g to 150 g of inventive mixtures are required per 100 kg of plant.
As stated above, compounds I and II present in the inventive mixtures are used in "effective amounts". This means that they are used in a quantity which allows to obtain the desired effect which is a synergistic increase of the health of a plant but which does not give rise to any phytotoxic symptom on the treated plant.
In all binary mixtures used according to the methods of the present invention, compound (I) and compound (II) are employed in amounts which result in a synergistic effect.
All inventive mixtures are typically applied as compositions comprising compound (I) and compound (II). In a preferred embodiment, the pesticial composition for increasing the health of a plant comprises a liquid or solid carrier and a mixture as described above.
For use according to the present invention, the inventive mixtures can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the mixtures accord- ing to the present invention. The formulations are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030,
GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961 ), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation Technology (Wiley VCH Verlag, Weinheim, 2001 ).
The agrochemical formulations may also comprise auxiliaries which are customary in agrochemical formulations. The auxiliaries used depend on the particular application form and active substance, respectively. Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations).
Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as N- methylpyrrolidone. Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. 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 and other solid carriers.
Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formal- dehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl- phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquid and proteins, denatured proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Swit- zerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvi- nylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof. Examples for thickeners (i.e. compounds that impart a modified flowability to formulations, i.e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kel- zan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).
Bactericides may be added for preservation and stabilization of the formulation. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie). Examples for suitable anti- freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Examples for anti-foaming agents are silicone emulsions (such as e.g. Silikon® SRE, Wacker, Ger- many or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples for tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).
Powders, materials for spreading and dusts can be prepared by mixing or concomi- tantly grinding the compounds (I) and/or (ll)and, if appropriate, further active substances, with at least one solid carrier.
Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., 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 and other solid carriers. Examples for formulation types are:
1 . Composition types for dilution with water
i) Water-soluble concentrates (SL, LS)
10 parts by weight of compounds of the inventive mixtures are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a formulation having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC)
20 parts by weight of compounds of the inventive mixtures are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. poly- vinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight.
iii) Emulsifiable concentrates (EC)
15 parts by weight of compounds of the inventive mixtures are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil eth- oxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight.
iv) Emulsions (EW, EO, ES)
25 parts by weight of compounds of the inventive mixtures are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil eth- oxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of compounds of the inventive mixtures are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of compounds of the inventive mixtures are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight.
vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of compounds of the inventive mixtures are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight.
viii) Gel (GF)
In an agitated ball mill, 20 parts by weight of compounds of the inventive mixtures are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.
2. Composition types to be applied undiluted
ix) Dustable powders (DP, DS)
5 parts by weight of compounds of the inventive mixtures are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight.
x) Granules (GR, FG, GG, MG)
0.5 parts by weight of compounds of the inventive mixtures is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight.
xi) ULV solutions (UL)
10 parts by weight of compounds of the inventive mixtures are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undi- luted having an active substance content of 10% by weight.
The agrochemical formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances. The compounds of the inventive mixtures are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
The compounds of the inventive mixtures can be used as such or in the form of their compositions, e.g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the compounds present in the inventive mixtures. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) 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 a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of compounds of the inventive mixtures . The compounds of the inventive mixtures may also be used successfully in the ultra- low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives. Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until
immediately prior to use (tank mix). These agents can be admixed with the compounds of the inventive mixtures in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1. Compositions of this invention may also contain fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.
The compounds contained in the mixtures as defined above can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
According to one embodiment of this invention, applying the compound (I) and compound (II) is to be understood to denote, that at least the compound (I) and compound (II) occur simultaneously at the site of action (i.e. plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow) in a effective amount.
This can be obtained by applying the compound (I) and compound (II) simultaneously, either jointly (e.g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance ap- plied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention. In the inventive mixtures, the weight ratio of the compounds generally depends from the properties of the compounds of the inventive mixtures. The compounds of the inventive mixtures can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts. In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition. E.g., kits may include the compound (I) and compound (II) and/or an adjuvant component and/or a further pesticidal compound (e.g. insecticide, fungicide or herbicide) and/or a growth regulator component). One or more of the components may already be com- bined together or p re-formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i.e., not pre-formulated. As such, kits may include one or more separate con- tainers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquid or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready-to-use spray liquid are applied per hectare of agricultural useful area, preferably 50 to 400 liters.
According to one embodiment, individual compounds of the inventive mixtures formu- lated as composition (or formulation) such as parts of a kit or parts of the inventive mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
In a further embodiment, either individual compounds of the inventive mixtures formu- lated as composition or partially premixed components, e.g. components comprising the compound (I) and compound (II) may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix). In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e.g. components comprising the compound (I) and compound (II) can be applied jointly (e.g. after tankmix) or consecutively.
When preparing the mixtures, it is preferred to employ the pure active compounds, to which further active compounds against pests, such as insecticides, herbicides, fungicides or else herbicidal or growth-regulating active compounds or fertilizers can be added as further active components according to need.
The inventive mixtures are employed by treating the plant, plant propagation material (preferably seed), soil, area, material or environment in which a plant is growing or may grow with an effective amount of the active compounds. Principally, the application rates of the inventive mixtures are from 0,3 g/ha to 2000 g/ha, preferably 5 g/ha to 2000 g/ha, more preferably from 50 to 900 g/ha, in particular from 50 to 900 g/ha.
When using glyphosate, the application rates are in the range of from 0,1 to 6,0 kg of active ingredient (acid equivalent) per hectare, depending on various parameters such as the weather conditions and the plant species.
As mentioned above, a variant of the present invention also comprises seed treatment with compound (II) followed by foliar spraying with compound (I).
Seed treatment can be made into the seedbox before planting into the field.
For seed treatment purposes, the weight ratio in the binary or ternary mixtures of the present invention generally depends on the properties of the compounds of the inven- tive mixtures.
Compositions, which are especially useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS)
D Emulsions (EW, EO, ES)
E Suspensions (SC, OD, FS)
F Water-dispersible granules and water-soluble granules (WG, SG)
G Water-dispersible powders and water-soluble powders (WP, SP, WS)
H Gel-formulations (GF)
I Dustable powders (DP, DS) These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation material (and also in furrow treatment). In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
In the treatment of plant propagation material (preferably seed), the application rates of the inventive mixture are generally for the formulated product (which usually comprises from 10 to 750 g/l of the active(s)).
The invention also relates to the propagation products of plants, and especially the seed comprising, that is, coated with and/or containing, a mixture as defined above or a composition containing the mixture of two or more active ingredients or a mixture of two or more compositions each providing one of the active ingredients. The plant propagation material (preferably seed) comprises the inventive mixtures in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material (preferably seed).
The separate or joint application of the compounds of the inventive mixtures is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.
The mixture of the invention is also suitable for combating animal pests, preferably invertebrate pests.
The term "invertebrate pest" as used herein encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
Invertebrate pests controlled by the mixture of the invention include for example: Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hip- pocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl- lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria;
dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hyso- cyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa;
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci; hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps,
Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactu- cae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus as- calonicus, Myzus cerasi, Myzus persicae, Myzus varians, Nasonovia ribis-nigri, Nila- parvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Sogatella furcifera Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus; Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
Siphonatera, e.g. Xenopsylla cheopsis, Ceratophyllus spp. The mixture of the invention is useful for the control of nematodes, especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species;
cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Het- erodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Paratylen- chus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Bur- rowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhyn- chus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus spe- cies; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
In a preferred embodiment of the invention the mixture of the invention is used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina. The mixture of the invention is particularly useful for controlling insects of the order Thysanoptera and Homoptera.
The mixtures of the present invention preferably show synergistic action with regard to the pests to be controlled or with regard to the plant-health effects. Synergism can be described as an interaction where the combined effect of a mixture of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect, in terms of percent effect, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20- 22): E = x + Y-^
100
In Colby's formula X and Y are the % control or the % effect observed for the individual compounds at a given concentration. E is the expected combined control/effect, which would be expected in the absence of synergism, if the compounds were applied together at the same concentrations of solo application. When the control/effect observed for the mixture (i.e. the observed combined control/effect) is greater than the expected combined control/effect (E) as calculated from Colby's formula, then the observed control or effect is synergistic.

Claims

Claims
A mixture comprising, as active ingredients,
1 ) at least one compound (I) selected from the group consisting of the compounds of following groups b1 ) to b15):
b1 ) the group of the lipid biosynthesis inhibitors selected from the group consisting of ACC-herbicides, namely alloxydim, alloxydim-sodium, butroxy- dim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P- methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop- P-tefury I, sethoxydim, tepraloxydim and tralkoxydim, and non ACC herbicides: namely benfuresate, butylate, cycloate, dala- pon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, moli- nate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;
b2) the group of the ALS inhibitors consisting of
sulfonylureas: selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimu- ron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfu- ron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron- methyl-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfu- ron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyra- zosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfo- sulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron,
imidazolinones: selected from the group consisting of imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr, triazolopyrimidine herbicides, and
sulfonamides: selected from the group consisting of cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam,
pyrimidinylbenzoates selected from the group consisting of bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac- methyl, pyrithiobac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2- pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1 -methylethyl ester (CAS 420138-41 -6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]- methyl]amino]-benzoic acid propyl ester (CAS 420138-40-5), N-(4- bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01 -8) and
sulfonylaminocarbonyl-triazolinone herbicides selected from the group consisting of flucarbazone, flucarbazone-sodium, propoxycarbazon, pro- poxycarbazon- sodium, thiencarbazone and thiencarbazone-methyl; b3) the group of the photosynthesis inhibitors selected from the group consisting of amicarbazone,
inhibitors of the photosystem II, selected from the group consisting of tri- azine herbicides, including chlorotriazine, triazinones, triazindiones, me- thylthiotriazines and pyridazinones such as ametryn, atrazine, chlorida- zone, cyanazine, desmetryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, propazin, simazin, simetryn, terbumeton, terbuthy- lazin, terbutryn and trietazin,
aryl urea compounds such as chlorobromuron, chlorotoluron, chloroxu- ron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, meta- mitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron,
phenyl carbamates such as desmedipham, karbutilat, phenmedipham and phenmedipham-ethyl,
nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters,
uraciles such as bromacil, lenacil and terbacil,
bentazon, bentazon-sodium, pyridate, pyridafol, pentanochlor and pro- panil and
inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-dimetilsulfate;
b4) the group of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, acifluorfen-sodium, azafenidin, ben- carbazone, benzfendizone, bifenox, butafenacil, carfentrazone, car- fentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flu- fenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidia- zimin, ethyl [3-[2-chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo- 1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31 -6; S-3100), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)- 5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452098-92-9),
N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl- 1 H-pyrazole-1 -carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6- fluoro-4-trifluoromethylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoro- methylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 45100-03- 7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1 ,4]oxazin-6- yl]-1 ,5-dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4-dione, 1 ,5-dimethyl-6- thioxo-3-(2 ,2 ,7-trif luoro-3-oxo-4-(prop-2-ynyl)-3 ,4-dihyd ro-2 H- benzo[b][1 ,4]oxazin-6-yl)-1 ,3,5-triazinane-2,4-dione, 2-(2,2,7-Trifluoro-3- oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4, 5,6,7- tetrahydro-isoindole-1 ,3-dione, and 1 -Methyl-6-trifluoromethyl-3-(2,2,7- trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-1 H- pyrimidine-2,4-dione;
b5) the group of the bleacher herbicides selected from the group consisting of PDS inhibitors selected from the group consisting of beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolina- fen and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)- pyrimidine (CAS 180608-33-7),
HPPD inhibitors selected from the group consisting of benzobicyclon, benzofenap, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyra- zoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone and bicyc- lopyrone,
bleacher, unknown target selected from the group consisting of acloni- fen, amitrole, clomazone and flumeturon;
b6) the group of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts;
b7) the group of the glutamine synthase inhibitors selected from the group consisting of bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and ist salts, in particular glufosinate-P or glufosinate-ammonium;
b8) the group of the DHP synthase inhibitors selected from the group consisting of asulam;
b9) the group of the mitose inhibitors selected from the group consisting of compounds of group K1 selected from the group consisting of dinitroanilines such as benfluralin, butralin, dinitramine, ethalfluralin, flu- chloralin, oryzalin, pendimethalin, prodiamine and trifluralin,
phosphoramidates such as amiprophos, amiprophos-methyl and bu- tamiphos,
benzoic acid herbicides such as chlorthal, chlorthal-dimethyl, pyridines such as dithiopyr and thiazopyr,
benzamides such as propyzamide and tebutam;
and compounds of group K2 selected from the group consisting of chlorpropham, propham and carbetamide;
b10) the group of the VLCFA inhibitors selected from the group consisting of chloroacetamides such as acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-
S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor, oxyacetanilides such as flufenacet and mefenacet,
acetanilides such as diphenamid, naproanilide and napropamide, tetrazolinones such as fentrazamide, and other herbicides such as anilo- fos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos and pyrox- asulfone;
the group of the cellulose biosynthesis inhibitors selected from the group consisting of chlorthiamid, dichlobenil, flupoxam, isoxaben, 1 -cyclohexyl- 5-pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3-ylamine and piperazine compounds of formula III,
Figure imgf000050_0001
in which
A is phenyl or pyridyl where Ra is attached in the ortho-position to the point of attachment of A to a carbon atom;
Ra is CN, N02, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy Ci-C4- haloalkoxy or D-C(=0)-Ra1 ;
Ry is d-Ce-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, NRARB or Ci-C4- haloalkyl and q is 0, 1 or 2;
RA,RB independently of one another are hydrogen, Ci-C6-alkyl, C3-C6- alkenyl and C3-C6-alkynyl; together with the nitrogen atom to which they are attached, RA,RB may also form a five- or six-membered saturated, partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S, which ring may be substituted by 1 to 3 groups Raa;
D is a covalent bond or Ci-C4-alkylene;
Ra1 is hydrogen, OH, Ci-C8-Alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl;
Raa is halogen, OH, CN, N02, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4- alkoxy, Ci-C4-haloalkoxy, S(0)qRy, D-C(=0)-Ra1 and tri-Ci-C4- alkylsilyl;
Rb independently of one another is CN, NO2, halogen, Ci-C4-alkyl, Ci- C4-haloalkyl, C2-C4-alkenyl, C3-C6-alkynyl, Ci-C4-alkoxy, Ci-C4- haloalkoxy, benzyl or S(0)qRy, or
Rb together with the group Ra or Rb attached to the adjacent ring atom may also form a five- or six-membered saturated or partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S, which ring may be partially or fully substituted by
Raa;
p is O orl ;
R30 is hydrogen, Ci-Ci2-alkyl, C3-Ci2-alkenyl, C3-Ci2-alkynyl, C1-C4- alkoxy or C(=0)R40, which can be partially or fully be substituted by Raa groups;
R40 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or C1-C4- haloalkoxy;
where in groups R30, Ra and their sub-substituents the carbon chains and/or the cyclic groups may carry 1 , 2, 3 or 4 substituents Raa and/or Ra1;
R31 is Ci-C4-alkyl;
R32 is OH, NH2, Ci-C4-alkyl, C3-C6-cycloalkyl, Ci-C4-haloalkyl or
C(=0)R25;
R25 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or C1-C4- halo-alkoxy
R33 is hydrogen, or R33 and R34 together are a covalent bond;
R34, R35, R36, R37 independently of one another are hydrogen;
R38, R39 independently of one another are hydrogen, halogen or OH; b12) the group of the decoupler herbicides selected from the group consisting of dinoseb, dinoterb and DNOC and its salts;
b13) the group of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters,
2,4-DB and its salts and esters, aminopy- ralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, fluroxypyr and its salts or esters, MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, and aminocyclopyrachlor and its salts and esters;
b14) the group of the auxin transport inhibitors selected from the group consisting of diflufenzopyr and its salts, naptalam and its salts;
b15) the group of the other herbicides consisting of bromobutide, chlorflure- nol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, di- fenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endo- thal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop- methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, indaziflam, ma- leic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tria- ziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4- pyridazinol (CAS 499223-49-3) and its salts and esters; and compound (II), which is the compound of formula II
Figure imgf000052_0001
The mixture according to claim 1 , wherein compound (I) is selected from the compounds of groups b1 ), b2, b3), b4), b5), b6), b7), b9), b10), b1 1 ), b13), b14) and b15) as defined in claim 1 .
3. The mixture according to claim 1 , wherein compound (I) is selected from the com- pounds of groups b1 ), b2, b3), b4), b5), b6), b7), b9), b10), b1 1 ), b13), b14) and b15) as defined below:
b1 ) the group of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P- butyl, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaqui- zafop, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxy- dim, tralkoxydim, benfuresate, dimepiperate, EPTC, esprocarb, etho- fumesate, molinate, orbencarb, prosulfocarb, thiobencarb and triallate; b2) the group of the ALS inhibitors selected from the group consisting of sulfonylureas: selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfu- ron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, ortho- sulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, prosulfu- ron, pyrazosulfuron-ethyl, rimsulfuron, sulfosulfuron, thifensulfuron- methyl, triasulfuron, trifloxysulfuron, triflusulfuron and tritosulfuron, midazolinones selected from the group consisting of imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr,
triazolopyrimidine herbicides and sulfonamides: selected from the group consisting of diclosulam, flumetsulam, florasulam, metosulam, penoxsu- lam, pyrimisulfan and pyroxsulam,
pyrimidinylbenzoates: selected from the group consisting of bispyribac- sodium, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac- sodium, flucarbazone-sodium, propoxycarbazon- sodium and thiencar- bazone-methyl;
b3) the group of the photosynthesis inhibitors selected from the group consisting of amicarbazone, ametryn, atrazine, chloridazone, cyanazine, he- xazinone, metribuzin, simazin, terbuthylazin and terbutryn, aryl urea such as chlorotoluron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron or thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, bromoxynil and its salts and esters, bentazon and bentazon-sodium, pyridate, propanil, di- quat, paraquat and paraquat-dichloride;
b4) the group of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, acifluorfen-sodium, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, cinidon-ethyl, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluorogly- cofen-ethyl, fomesafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, pyraflufen-ethyl, saflufenacil, sulfentrazone, ethyl [3-[2- chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31 - 6; S-3100), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H- benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl-6-thioxo-[1 ,3,5]triazinan-2,4-dione, 1 ,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro- 2H-benzo[b][1 ,4]oxazin-6-yl)-1 ,3,5-triazinane-2,4-dione, 2-(2,2,7- trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)- 4,5,6,7-tetrahydro-isoindole-1 ,3-dione, and 1 -methyl-6-trifluoromethyl-3- (2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6- yl)-1 H-pyrimidine-2,4-dione;
b5) the group of the bleacher herbicides selected from the group consisting of PDS inhibitors selected from the group consisting of diflufenican, flu- rochloridone and picolinafen,
HPPD inhibitors: selected from the group consisting of benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tefuryltrione, tembotrione, toprame- zone and bicyclopyrone, and other bleachers: selected from the group consisting of aclonifen, ami- trole, clomazone and flumeturon;
b6) the group of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts;
b7) the group of the glutamine synthase inhibitors selected from the group consisting of glufosinate and its salts;
b9) the group of the mitose inhibitors consisting of compounds of group K1 selected from the group consisting of
dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin and triflu- ralin,
pyridines: dithiopyr and thiazopyr;
b10) the group of the VLCFA inhibitors selected from the group consisting of chloroacetamides : acetochlor, alachlor, butachlor, dimethenamid, di- methenamid-P, metazachlor, metolachlor, metolachlor-S, pretilachlor, and thenylchlor,
oxyacetanilides: flufenacet and mefenacet,
tetrazolinones: fentrazamide,
and other herbicides: cafenstrole, fenoxasulfone, ipfencarbazone andpy- roxasulfone;
b1 1 ) the group of the cellulose biosynthesis inhibitors selected from the group consisting of isoxaben, 1 -Cyclohexyl-5-pentafluorphenyloxy-14- [1 ,2,4,6]thiatriazin-3-ylamine and piperazine compounds of formula III as defined in claim 1 ;
b13) the group of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, aminopyralid, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr and its salts or esters, MCPA and its salts and esters, MCPB and its salts and esters, me- coprop and its salts and esters, mecoprop-P and its salts and esters, pi- cloram and its salts and esters, quinclorac, quinmerac, triclopyr and its salts and esters, and aminocyclopyrachlor and its salts and esters;
b14) the group of the auxin transport inhibitors selected from the group consisting of diflufenzopyr, and its salts;
b15) compounds selected from the group consisting of cinmethylin, dymron, indanofan, indaziflam, oxaziclomefone and triaziflam.
4. The mixture according to claim 1 , wherein compound (I) is selected from the compounds of groups b1 ), b2, b3), b4), b5), b6), b7), b9), b10), b1 1 ), b13), b14) and b15) as defined below:
b1 ) the group of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, fenoxaprop-P-ethyl, fluazifop-P-butyl, haloxyfop-P-methyl, pinoxaden, profoxydim, sethoxydim, tepraloxydim, tralkoxydim, esprocarb, prosulfo- carb, thiobencarb and triallate;
b2) the group of the ALS inhibitors selected from the group consisting of sulfonylureas: selected from the group consisting of bensulfuron-methyl, chlorimuron-ethyl, cyclosulfamuron, flupyrsulfuron-methyl-sodium, fo- ramsulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metazosulfuron, nicosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfo- sulfuron, and tritosulfuron,
imidazolinones such as imazamethabenz, imazamethabenz-methyl, ima- zamox, imazapic, imazapyr, imazaquin or imazethapyr,
triazolopyrimidine herbicides and sulfonamides: selected from the group consisting of diclosulam, flumetsulam, florasulam, penoxsulam and py- roxsulam,
pyrimidinylbenzoates: selected from the group consisting of bispyribac- sodium, pyribenzoxim, pyriftalid, propoxycarbazon- sodium and thien- carbazone-methyl;
b3) the group of the photosynthesis inhibitors selected from the group consisting of ametryn, atrazine, cyanazine, hexazinone, metribuzin, simazin, terbuthylazin and terbutryn,
aryl urea compounds such as diuron, fluometuron or isoproturon, phenyl carbamates such as bromoxynil and its salts and esters, bentazon, propanil, paraquat and paraquat-dichloride;
b4) the group of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, acifluorfen-sodium, flumioxazin, fo- mesafen, lactofen, oxyfluorfen, saflufenacil, sulfentrazone, ethyl [3-[2- chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate, 2-(2,2,7-trifluoro- 3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4,
5,6,7- tetrahydro-isoindole-1 ,3-dione, and 1 -methyl-6-trifluoromethyl-3-(2,2,7- trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-1 H- pyrimidine-2,4-dione;
b5) the group of the bleacher herbicides selected from the group consisting of PDS inhibitors selected from the group consisting of diflufenican, flu- rochloridone, picolinafen,
HPPD inhibitors: selected from the group consisting of benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tefuryltrione, tembotrione, toprame- zone and bicyclopyrone, and
other bleachers: selected from the group consisting of amitrole and clo- mazone;
b6) the group of the EPSP synthase inhibitors selected from the group consisting of glyphosate and its salts; b7) the group of the glutamine synthase inhibitors selected from the group consisting of glufosinate and its salts;
b9) the group of the mitose inhibitors selected from the group consisting of compounds of group K1 consisting of pendimethalin and trifluralin;
b10) the group of the VLCFA inhibitors selected from the group consisting of chloroacetamides: selected from the group consisting of acetochlor, di- methenamid-P, metazachlor, metolachlor, metolachlor-S and preti- lachlor,
oxyacetanilides: selected from the group consisting of flufenacet and mefenacet,
the tetrazolinone fentrazamide,
and other herbicides selected from the group consisting of cafenstrole, fenoxasulfone and pyroxasulfone;
b1 1 ) the group of the cellulose biosynthesis inhibitors selected from the group consisting of isoxaben, 1 -cyclohexyl-5-pentafluorphenyloxy-14-
[1 ,2,4,
6]thiatriazin-3-ylamine and piperazine compounds of formula III as defined in claim 1 ;
b13) the group of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, aminopyralid and its salts, clopyralid and its salts and esters, dicamba and its salts and esters, fluroxypyr-meptyl,
MCPA, MCPB and its salts and esters, mecoprop and its salts and esters, quinclorac and quinmerac;
b14) diflufenzopyr;
b15) compounds selected from the group consisting of cinmethylin, dymron, indanofan, indaziflam, oxaziclomefone and triaziflam.
The mixture according to claim 1 , wherein compound (I) is selected from the group consisting of the compounds of the groups b1 ), b2), b3), b4), b5), b6), b7), b9), b10), b1 1 ), b13) and, b14) as defined in claim 4 and the compoundindaziflam.
The mixture according to claim 1 , wherein compound (I) is selected from the group consisting of the compounds of the groups b1 ), b2), b3), b4), b5), b6), b9), b10), b1 1 ), b13) and b15) defined below: b1 ) the group of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim, pinoxaden, pro- foxydim, sethoxydim, tepraloxydim and tralkoxydim;
b2) the group of the ALS inhibitors selected from the group consisting of sulfonylureas: selected from the group consisting of chlorimuron-ethyl, foramsulfuron, nicosulfuron, rimsulfuron and tritosulfuron,
midazolinones selected from the group consisting of imazamox, ima- zapic, imazapyr, imazaquin and imazethapyr, pyrimidinylbenzoates: selected from the group consisting of pyriben- zoxim and pyriftalid;
b3) the group of the photosynthesis inhibitors selected from the group consisting of ametryn, atrazine, cyanazine, simazin, terbuthylazin, aryl urea selected from the group consisting of diuron and isoproturon, phenyl carbamates selected from the group consisting of bromoxynil and its salts and esters, and bentazon;
b4) the group of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, fomesafen, saflufenacil and sulfen- trazone;
b5) the group of the bleacher herbicides selected from the group consisting of the PDS inhibitor picolinafen,
HPPD inhibitors: selected from the group consisting of benzobicyclon, isoxaflutole, mesotrione, sulcotrione, tembotrione and topramezone, and the other bleacher: clomazone;
b6) the group of the EPSP synthase inhibitors selected from the group consisting of glyphosate, glyphosate-isopropylammonium, glyphosate- diammonium and glyphosate-trimesium (sulfosate);
b9) the group of the mitose inhibitors selected from the group consisting of pendimethalin; or from
b10) the group of the VLCFA inhibitors selected from the group consisting of chloroacetamides selected from the group consisting of acetochlor, di- methenamid-P, metazachlor, metolachlor, metolachlor-S and preti- lachlor,
the oxyacetanilide flufenacet
the tetrazolinone fentrazamide,
and pyroxasulfone;
b13) the group of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, clopyralid and its salts and esters, dicam- ba and its salts and esters, MCPA, quinclorac and quinmerac;
b15) indaziflam.
7. The mixture according to claim 1 , wherein compound (I) is selected from the
group consisting of the compounds of the groups b1 ), b2), b3), b4), b5), b6), b9), b10), b1 1 ), b13) and b15) defined below: b1 ) the group of the lipid biosynthesis inhibitors selected from the group consisting of clethodim, clodinafop-propargyl, cycloxydim and pinoxaden; b2) the group of the ALS inhibitors selected from the group consisting of sulfonylureas: selected from the group consisting of nicosulfuron and tri- tosulfuron, midazolinones selected from the group consisting of imazamox, ima- zapic, imazaquin and imazethapyr,
pyrimidinylbenzoates selected from the group consisting of pyribenzoxim and pyriftalid;
b3) the group of the photosynthesis inhibitors selected from the group consisting of atrazine, simazin, terbuthylazin,
aryl urea compounds selected from the group consisting of diuron and isoproturon,
phenyl carbamates selected from the group consisting of bromoxynil and its salts and esters
and bentazon;
b4) the group of the protoporphyrinogen-IX oxidase inhibitors selected from the group consisting of acifluorfen, fomesafen and saflufenacil;
b5) the group of the bleacher herbicides: selected from the group consisting of the PDS inhibitor picolinafen,
HPPD inhibitors: selected from the group consisting of mesotrione, sul- cotrione, tembotrione and topramezone, and
the other bleacher;
b6) the group of the EPSP synthase inhibitors selected from the group con- sisting of glyphosate, glyphosate-isopropylammonium and glyphosate- trimesium (sulfosate);
b9) the mitose inhibitor pendimethalin;
b10) the group of the VLCFA inhibitors selected from the group consisting of chloroacetamides selected from the group consisting of acetochlor, di- methenamid-P and metazachlor, and
the oxyacetanilide flufenacet;
b13) the group of the auxin herbicides selected from the group consisting of 2,4-D and its salts and esters, dicamba and its salts and esters, MCPA and quinclorac;
b15) indaziflam.
8. The mixture of any of claims 1 to 7, wherein compound I and compound II are present in synergistically effective amounts.
9. The mixture of any of claims 1 to 8, wherein compound I and compound II are present in a weight ratio of from 1 :200 to 200:1.
10. The mixture of any of claims 1 to 8, wherein compound I and compound II are present in a weight ratio of from 1 :100 to 100:1 .
1 1 . A pesticidal composition, comprising a liquid or solid carrier and a mixture as defined in any of claims 1 to 10.
12. The use of a mixture as claimed in any of claims 1 to 10 for improving the health of plants.
13. The use of a mixture as claimed in any of claims 1 to 10 for increasing the yield of a plant.
14. A method for improving the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with an effective amount of a mixture as defined in any of claims 1 to 10.
A method for increasing the yield of a plant, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows is treated with an effective amount of a mixture as defined in any of claims 1 to 10.
The use or method according to any of claims 12 to 14, wherein the plant is selected from soybean, wheat, sunflower, canola, oilseed rape, corn, cotton, sugar cane, juncea, peas, lentils, alfalfa, vine, fruits and vegetables.
17. The use or method according to any of claims 12 to 16, wherein the plant is a herbicide tolerant plant.
18. The use or method according to any of claims 12 to 17, wherein compound I and compound II as defined in any of claims 1 to 10 are applied simultaneously, that is jointly or separately, or in succession.
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