Synergistic herbicidal composition containing the chloroacetanilids and picolinic acids

The invention relates to a synergistic herbicidal mixture / composition comprising (a) a herbicidal chloroacetanilide component, and (b) a mixture of a herbicidal component of picolinic acid.

Protecting crops from weeds and other vegetation that inhibits the development of crops is still a current problem in agriculture. To help overcome this problem, chemical synthesis scientists have produced a large number of compounds and preparations effective in controlling such undesirable development. Various chemical herbicide compounds have been disclosed in the literature, and an enormous amount is in commercial use.

In some cases, herbicidal active ingredients have been shown to be more effective in combination than when used alone, this is referred to as synergism. As described in "Herbicide Handbook Weed Science Society of America, 17th Edition, 1994, p. 318", "synergism [is] such an interaction of two or more factors that when combined their effect is greater than the effect predicted. based on the response for each factor used separately. The present invention is based on the discovery that certain chloroacetanilides and certain picolinic acids, individually known for their herbicidal effectiveness, show synergistic effects when used in combination.

In the art, the herbicidal compounds forming the synergistic composition of the invention are independently known to act on plant development.

Chloroacetanilides are a known class of compounds with herbicidal activity. Many herbicidal chloroacetanilide compounds are described in The Pesticide Manual, 14th Edition, 2006, including 2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6-methylphenyl) -acetamide (acetochlor), 2-chloro -N- (2,6-diethylphenyl) -N- (methoxymethyl) acetamide (alachlor), N- (butoxymethyl) -2-chloro-N- (2,6-diethylphenyl) acetamide (butachlor), 2-chloro-N - (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) -acetamide (metolachlor), 2-chloro-N- (1-methyl-ethyl) -N-phenylacetamide (propachlor), 2-chloro-N- (2,4-dimethyl-3-thienyl) -N - [(1S) -2-methoxy-1-methyloethyl] -acetamide (dimethenamid P) and 2-chloro-N- (2,6 -dimethylphenyl) -N- (1H-pyrazol-1-ylmethyl) acetamide (metazachlor). Many of these chloroacetanilide herbicides are commercially available.

Picolinic acids are also a known class of compounds with herbicidal activity. Many picolinic acid derivatives are described in the Pesticide Manual, 14th Edition, 2006, including 3,6-dichloro-2-pyridine carboxylic acid (clopyralid), 4-amino-3,5,6-trichloro-2-pyridine carboxylic acid ( picloram) and 4-amino-3,6-dichloro-2-pyridine carboxylic acid (aminopyralid). Many picolinic acid herbicides are commercially available.

The invention relates to a herbicidal mixture which comprises a herbicidally effective amount of (a) a chloroacetanilide compound selected from acetochlor or metazachlor, and (b) a mixture of the picolinic acid derivative of clopyralid picloram and aminopyralid, or a mixture of clopyralid and picloram, the weight ratio of the chloroacetanilent component to picolinic acid is between 500: 1 and 6: 1.

The invention also relates to a herbicidal composition which comprises a herbicidally effective amount of the above herbicidal mixture and an agriculturally acceptable adjuvant or carrier.

The invention also relates to a method of controlling undesirable vegetation which comprises contacting vegetation, or its locus, or applying to a soil to prevent development of such vegetation, with a herbicidally effective amount of a herbicidal mixture as defined above.

The control of the growth of undesirable vegetation is carried out in particular in cereals.

The spectrum of plant species for the compounds of the synergistic mixture, i.e. the weed species controlled by the respective compounds, is broad and very significant. Chloroacetanilides like acetochlor control annual grass weeds and certain broadleaf weeds, including Amaranthus spp and Solanum spp. Picolinic acids like clopyralid and picloram control Compositae and Amaranthaceae broadleaf weeds with some activity against Chenopodiaceae and Polygonaceae. However, it was unexpectedly found that the claimed combination shows a synergistic effect in the control of quinoa (chenopodium album L; CHEAL), buckwheat (polygonum convolvulus L; POLCO), knotweed (polygonum aviculare; POLAV), violet (viola arvensis L; VIOAR), clinging ( galium aparine L; GALAP) and poppies (papaver rhoeas L; PAPRH) in doses lower than single doses

Compounds. The claimed synergistic mixtures are particularly useful for controlling weeds in cereals and oilseed rape.

The term herbicide is used herein to mean an active ingredient that destroys, controls or otherwise deleteriously modifies plant growth. A herbicidally effective amount, or a vegetation controlling amount, is that amount of the active ingredient which produces an adverse modifying effect and includes deviation from natural development, destruction, regulation, drying out, inhibition of growth, and the like. The terms plant and vegetation include germinating seeds, germinating plants, and plants in full vegetation.

Herbicidal activity is demonstrated by the compounds of the synergistic mixture when they are applied directly to the plant or to its place of occurrence, at any stage of growth, or before planting or sprouting. The observed effect depends on the plant species whose development is to be controlled, the stage of plant development, the application parameters of the solution and the size of the sprayed droplets, the particle size of the solid components, the environmental conditions at the time of application, the specific compound used, the specific adjuvants and carriers used. , soil type, and the like, as well as the amount of chemicals used. These and other factors can be modified as is known in the art to contribute to non-selective or selective herbicidal action. In general, it is preferred to apply the compositions of the invention post-emergence to relatively immature undesirable vegetation to obtain maximum weed control.

In the composition of the invention, the weight ratio of chloroacetanilide component to picolinic acid component for synergistic herbicidal action is between 500: 1 and 6: 1. Preferably, the weight ratio of the chloroacetanilide component to the picolinic acid component is between 200: 1 and 8: 1, particularly preferably between 180: 1 and 11: 1.

The dose of the synergistic composition employed will depend on the particular type of weed to be controlled, the degree of control required, and the time and mode of application. In general, the composition according to the invention is applied at a rate of between 0.05 and 5 kg / ha, based on the total amount of active ingredients of the composition. A rate of between 0.5 and 3 kg / ha is preferred. In a particularly preferred embodiment, the chloroacetanilide component is applied at a rate of between 1 and 2 kg / ha and the picolinic acid component is applied at a rate of between 0.005 and 0.3 kg / ha.

The components of the synergistic mixture according to the invention can be used either alone or as part of a multi-component herbicidal system.

The synergistic mixture of the invention may be used in combination with one or more other herbicides to control a variety of undesirable plants. When used in combination with other herbicides, the composition may be formulated with another herbicide or herbicides, by tank mixing with another herbicide or herbicides, or sequentially applied with another herbicide or herbicides. Certain herbicides that can be used in conjunction with the synergistic composition of the present invention include: amide herbicides such as allidochlor, beflubutamide, benzadox, benzipram, bromobutide, kafenstrol, CDEA, chlortiamide, cyprazole, dimethenamid, P-dimethenamid, diphenamid, epronidase, etnipromide. , flupoxam, fomesafen, halosafen, isocarbamide, isoxaben, napropamide, naptalam, petoxamide, propyzamide, quinonamide, and tebutam; anilide herbicides such as chloranocryl, cisanilide, clomeprop, cypromide, diflufenican, etobenzanide, fenasulam, flufenacet, flufenican, mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanochlor, picolinafen, and propanilide; arylalanine herbicides such as benzoolprop, flamprop and flamprop-M; sulfonanilide herbicides such as benzofluorine, perfluidone, pyrimisulfan and profluazole; sulfonamide herbicides such as asulam, carbasulam, fenasulam and oryzalin; antibiotic herbicides like bilanaphos; benzoic acid herbicides such as chloramben, dicamba, 2,3,6-TBA and tricamba; pyrimidinylbenzoic acid herbicides such as bispyribac and pyriminobacter; pyrimidinylthiobenzoic acid herbicides such as pyrithiobacterium; phthalic acid herbicides such as chlorthal; picolinic acid herbicides such as aminopyralid, clopyralid and picloram; quinolinecarboxylic acid herbicides such as chinklorac and quinmerac; arsenic herbicides such as cacodylic acid, CMA, DSMA, hexaflurate, MAA, MAMA, MSMA, potassium arsenite, and sodium arsenite; benzoylcyclohexanedione herbicides such as mesotrione, sulcotrione, tefuryltrione and tembotrione; benzofuranylalkylsulfonate herbicides such as benfuresate and ethofumesate; carbamate herbicides such as asulam, carboxazole, chlorprocarb, dichlormate, fenasulam, carbutilate and terbucarb; carbanilin herbicides such as barban, BCPC, carbasulam, carbetamide, CEPC, chlorbufam, chlorpropham, CPPC, desmedipham, phenisophham, phenmedipham, phenmediphamethyl, propham and swep; cyclohexene oxime herbicides such as alloxydim, butroxydim, clethodim, cloproxydim, cycloxydim, propoxydim, sethoxydim, tepraloxydim

And tralkoxydim; cyclopropylisoxazole herbicides such as isoxachlortol and isoxaflutole; dicarboximide herbicides such as benzfendisone, cinidone-ethyl, flumezin, flumiclorac, flumioxazin and flumipropin; dinitroaniline herbicides like benfluralin, butralin, dinitramine, etalfluralin, fluchloralin, isopropalin, metalpropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin and trifluralin; dinitrophenol herbicides like dinophenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, etinophen and medinoterb; diphenylether herbicides such as ethoxyfen; Nitrophenylether herbicides such as acifluorfen, aclonifene, bifenox, chlomethoxifene, chlornitrofen, etnipromide, fluorodifene, fluoroglycophen, fluoronitrophene, fomesafen, furyloxifene, halosaphene, lactophene, nitrofen, nitrofluorfen and oxyfluorfen; dithiocarbamate herbicides such as dazomet and metam; halogenated aliphatic herbicides such as alorac, chloropone, dalapone, flupropanate, hexachloroacetone, iodomethane, methyl bromide, monochloroacetic acid, SMA and TCA; imidazolinone herbicides such as imazametabenz, imazamox, imazapic, imazapyr, imazaquin and imazethapyr; inorganic herbicides such as ammonium sulfamate, borax, calcium chlorate, copper sulfate, iron sulfate, potassium azide, potassium cyanate, sodium azide, sodium chlorate and sulfuric acid; nitrile herbicides such as bromobonil, bromoxynil, chloroxynil, dichlobenil, iodobonil, ioxynil and pyraclonil; organophosphorus herbicides such as amiprofos-methyl, anilophos, bensulide, bilanaphos, butamiphos, 2,4-DEP, DMPA, EBEP, fosamine, glufosinate, glyphosate and piperophos; phenoxy herbicides such as bromophenoxime, clomeprop, 2,4-DEB, 2,4-DEP, diphenopentene, disul, erbon, etnipromide, penteracol and trifopsime; phenoxyacetic herbicides such as 4-CPA, 2,4-D, 3,4-DA, MCPA, MCPA-thioethyl and 2,4,5-T; phenoxybutane herbicides such as 4-CPB, 2, 4-DB, 3,4-DB, MCPB and 2,4,5-TB; phenoxypropionic herbicides such as cloprop, 4-CPP, dichlorprop, dichlorprop-P, 3,4-DP, fenoprop, mecoprop and mecoprop-P; aryloxyphenoxypropionic herbicides such as chlorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop, fenoxaprop-P, fentiaprop, fluazifop, fluazifop-P, haloxyfop, haloxyfop-P, isoxapyrifop, meta-phalchophop, and chisalchopophop; phenylenediamine herbicides such as dinitramine and prodiamine; pyrazolyl herbicides such as benzofenap, pyrazolinate, pyrazulfotol, pyrazoxifene, pyroxasulfone and toprameson; pyrazolylphenyl herbicides such as fluazolate and pyraflufen; pyridazine herbicides such as credazin, pyridafol and pyridate; pyridazinone herbicides such as brompirazone, chloridazone, dimidazone, flufenpyr, metflurazone, norflurazone, oxapirazone and pidanone; pyridine herbicides such as cliodinate, dithiopyr, flurocspyr, haloxidine, picolinafen, pyriclor, thiazopyr and triclopyr; pyrimidinediamine herbicides such as iprimidam and thioclorim; quaternary ammonium herbicides such as cyperquat, diethamquat, difenzoquat, diquat, morphamquat and paraquat; thiocarbamate herbicides such as butylate, cyclohe, di-allate, EPTC, esprocarb, ethiolate, isopolinate, methiobencarb, molinate, orbencarb, pebulate, prosulfocarb, pyrogenicarb, sulfallate, thiobencarb, thiocarbazil, tri-allate; thiocarbonate herbicides such as dimexane, EXD and proxane; thiourea herbicides such as metiuron; triazine herbicides such as dipropetryn, triaziflam and trihydroxytriazine; chlorotriazine herbicides such as atrazine, chlorazine, cyanazine, cyprazine, eglinin, ipazine, mesoprazine, procyazin, proglinin, propazine, sebutylazine, simazine, terbutylazine and triethazine; methoxytriazine herbicides such as atraton, methomethone, prometon, secbumeton, simeton and terbumeton; methylthiotriazine herbicides such as amethrin, aziprotrin, cyanathrin, desmethrin, dimethamethrin, methoprotrin, promethrin, simethrin and terbuthrin; triazinone herbicides such as ametridione, amibuzin, hexazinone, isomethiosin, metamitron and metribuzin; triazole herbicides such as amitrole, cafenstrol, epronase and flupoxam; triazolone herbicides such as amicarbazone, bencarbazone, carfentrazone, flucarbazone, propoxycarbazone, sulfentrazone and methyl thiencarbazone; triazolopyrimidine herbicides such as cloransulam, diclosulam, florasulam, flumetsulam, metosulam, penoxulam and piroxulam; uracil herbicides such as butafenacil, bromacil, flupropacil, isocil, lenacil, saflufenacil and terbacil; 3-phenyluracils; urea herbicides such as benzthiazuron, cumyluron, cycluron, dichloralurea, diflufenzopyr, isonoruron, isouron, metabenzthiazuron, monizouron and noruron; phenylurea herbicides, such as anizuron, buturon, chlorbromuron, chlorethuron, chlorotoluron, chloroxuron, daimuron, difenoxuron, dimefuron, diuron, fenuron, fluometuron, fluotiuron, isoproturon, iinuron, metiuron, methromuron, methromuron, methromurimolin parafuron, phenobenzuron, siduron, tetrafluron and thidiazuron; pirymidynylosulfonylomocznikowe herbicides such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, mesosulfuron, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, pyrazosulfuron, rymsulfuron, sulfometuron, sulfosulfuron and trifloxysulfuron; triazinylsulfonylurea herbicides such as chlorsulfuron, cinosulfuron, ethametsulfuron, iodosulfuron, metsulfuron, prosulfuron, thifensulfuron, triasulfuron, tribenuron, triflusulfuron and tritosulfuron; thiadiazolylurea herbicides such as butiuron, etidimuron, tebuthiuron, thiazafluron and thidiazuron; and unclassified herbicides such as acrolein, allyl alcohol, azafenidine, benazoline, bentazone, benzobicyclone, butidazole, calcium cyanamide,

PL 217 747 B1 cambendichlor, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, cinnmethylin, clomazone, CPMF, cresol, ortho-dichlorobenzene, dimepiperate, endotal, fluoromidine, fluridone, flurochloridone, flurtammon, flutiacet, indium methylophenanyl , oxadiargil, oxadiazone, oxazyclomephone, pentachlorophenol, pentoxazone, copper phenyl acetate, pinoxaden, prosulfalin, pyribenzoxime, pyriphthalide, quinoclamine, rhodetanil, sulglicapine, thidiazine, tridifan, trimethuron, tripropindane and tritak.

Furthermore, the synergistic composition of the invention may be used in combination with glyphosate, glufosinate, 2,4-D or dicamba, on glyphosate, glufosinate, 2,4-D or dicamba tolerant cereals. In general, it is preferred to use the synergistic composition of the invention in combination with herbicides which are selective for the treated cereals and which complete the spectrum of weeds controlled by these compounds at the rate applied. Furthermore, it is generally preferred to apply the synergistic composition of the invention and the other complementary herbicides at the same time, either in the form of a combined combination or as a tank mix.

The synergistic composition of the invention can generally be used in combination with known herbicidal saifers such as benoxacor, bentiocarb, brassinolide, cloquintocet (mexyl), cyometrinil, daimuron, dichlormide, dicyclonone, dimepiperate, disulfoton, fenchlorazolimolphenurol, flophenurate. , isoxadifen-ethyl, mefenpirdiethyl, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenylsulfonylbenzoic acid amides, to increase their selectivity.

In practice, it is preferred to use the synergistic composition of the invention in mixtures containing a herbicidally effective amount of the herbicidal components together with at least one agriculturally acceptable adjuvant or carrier. Suitable adjuvants or carriers should not be phytotoxic to the cereals, particularly at the concentrations employed in applying the composition to selectively control weeds in the presence of the cereals, and should not chemically react with the herbicidal components or other components of the composition. Such mixtures may be intended to be applied directly to weeds or their locus, or they may be concentrates or formulations which are normally diluted with additional carriers and adjuvants prior to application. They can be solid, such as, for example, dusts, granules, water-dispersible granules or wettable powders, or liquid, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions.

Suitable agricultural adjuvants and carriers that are useful in making the herbicidal mixtures of the invention are well known to those skilled in the art.

Liquid carriers that can be used include water, toluene, xylene, petroleum, grain oil, acetone, methyl ethyl ketone, cyclohexanone, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol methyl ethanol, ethanol ethanol and ethylene glycol. , isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, and the like. In general, water is the solvent of choice for the dilution of concentrates.

Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgite clay, kaolin clay, diatomaceous earth, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller earth, cotton seed husks, wheat flour, soybean meal, pumice, wood flour, walnut husk meal, lignin, and the like.

In general, it is desirable to include one or more surfactants in the compositions of the invention. Such surfactants are advantageously used in both solid and liquid compositions, especially intended to be diluted with a carrier before use. Surfactants can be anionic, cationic or non-ionic and can be used as emulsifying, wetting, suspending, or other purpose.

Typical surfactants include salts of alkyl sulfates such as diethanol ammonium lauryl sulfate; alkylarylsulfonate salts such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as ethoxylated nonylphenol-C18; alcohol-alkylene oxide addition products such as ethoxylated C16 tridecyl alcohol; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts such as sodium di (2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitan oleate; quaternary amines such as lauryl trimethyl ammonium chloride; polyethylene glycol fatty acid esters, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and monodialkylphosphate esters.

PL 217 747 B1

Other adjuvants widely used in agricultural compositions include compatibilizing, antifoaming, sequestering, neutralizing and buffering agents, corrosion inhibitors, dyes, perfumes, sprays, penetration enhancers, adhesives, dispersants, thickeners, freezing point depressants, antimicrobials, and the like. . The compositions can also include other compatible components, e.g. other herbicides, plant growth regulators, fungicides, insecticides, and the like, furthermore may be formulated with liquid or solid fertilizers, particulate fertilizer carriers like ammonium nitrate, urea and the like.

In general, the concentration of the active ingredients in the synergistic composition according to the invention is 0.001-98% by weight. Concentrations of 0.01-90% by weight are often used. In compositions used as concentrates, the active ingredients are generally present in an amount from 5-98% by weight, more preferably 10-90% by weight. Such compositions are typically diluted with an inert carrier, such as water, before use. The diluted compositions are typically applied to weeds or the locus of weeds, generally as compositions containing 0.0001-1% by weight of active ingredient, and preferably 0.001-0.05% by weight.

The compositions herein can be applied to weeds or their locus using conventional ground or air dusters, sprays, and granule applicators, in addition to irrigation water, and other conventional means known to those skilled in the art.

The following examples illustrate the present invention.

Examples

To evaluate weed control, field trials were conducted with early post-emergence herbicides in maize fields. Each trial was run as a standardized complete trial with triplicate for each treatment on plots ranging in size from 2.5 x 6.5 m to 3.0 x 8.0 m. In these trials, herbicidal treatments included:

acetochlor at a dose of 1680 g / ha clopyralid + picloram at a dose of 93.5 + 23.5 g / ha clopyralid + picloram + aminopyralid at a dose of 72 + 24 + 12 g / ha acetochlor + clopyralid + picloram at a dose of 1680 + 93.5 + 23.5 g / ha acetohlor + clopyralid + picloram + aminopyralid at the dose of 1680 + 72 + 24 + 12 g / ha

Herbicides were sprayed post-emergence on the 1-3 leaf stage and the weeds stage

1-2 leaves. The acetochlor preparation used also contained a furylazol sachet.

Weed control rate was visually assessed and recorded 40 to 71 days after application as a percentage of weed control. Damage percentages represent overall plant damage due to all factors including: growth inhibition, developmental abnormalities, chlorosis, necrosis, growth inhibition, and other types of plant damage. Destruction ranges from 0-100%, where 0 means no damage and 100 means complete failure.

Combinations of acetochlor in mixtures with clopyralid + picloram or clopyralid + picloram + aminopyralid have been found to show unexpected and unexpected synergistic effects in controlling CHEAL, POLAV and POLCO, while acetochlor alone, clopyralid + picloram alone, or clopyralid + picloram + alone aminopyralid do not provide acceptable control of these species.

Table 1 below shows the results of the above-described early post-emergence testing of the combination of acetochlor with clopyralid + picloram on CHEAL, POLAV and POLCO. Table 1 also shows the expected weed control for the tested combinations of acetochlor with clopyralid + picloram against CHEAL, POLAV and POLCO, results calculated by the Colby method (SR Colby publication. Calculating Synergistic and Antagonistic Response of Herbicide Combinations. WEEDS 15 (1): 20- 23, 1967). The Colby method is a direct measure of the synergistic activity of two herbicides. According to the Colby method:

E = X + Y (ΧΥ / 100), where E is the expected% weed control for the combination of the first H1 and second H2 herbicides at the rate applied, p + qg / ha; X is the% weed control found for H1 when applied at a rate of pg / ha; and Y is the% weed control found for H2 when applied at qg / ha.

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Table 1

Early post-emergence weed control

<td>Code of the weed according to Bayer</td><td>clopyralid + picloram</td><td>acetochlor</td><td>acetochlor + clopyralid + picloram</td><td>calculated according to Colby</td><td>difference</td>

<td></td><td>93 + 23 g ai / ha</td><td>1680 g ai / ha</td><td>1680 + 93 + 23g ai / ha</td><td></td><td></td>

<td>CHEAL</td><td> 53</td><td> 47</td><td> 98</td><td> 76</td><td> 22</td>

<td>CHEAL</td><td> 70</td><td> 52</td><td> 99</td><td> 85</td><td> 14</td>

<td>POLAV</td><td> 50</td><td> 58</td><td> 90</td><td> 79</td><td> 11</td>

<td>POLAV</td><td> 60</td><td> 52</td><td> 95</td><td> 81</td><td> 14</td>

Table 2 below shows the results of the above-described early post-emergence acetochlor + clopyralid + picloram + aminopyralide combination test on CHEAL and POLAV. Table 2 also shows the expected weed control for the tested combinations of acetochlor with clopyralid + picloram + aminopyralid against CHEAL and POLAV, calculated by the Colby method.

Table 2

Early post-emergence weed control

<td>Code of the weed according to Bayer</td><td>clopyralid + picloram + aminopyralid</td><td>acetochlor</td><td>acetochlor + clopyralid + picloram + aminopyralid</td><td>calculated according to Colby</td><td>difference</td>

<td></td><td>72 + 24 + 12g ai / ha</td><td>1680 g ai / ha</td><td>1680 + 72 + 24 + 12 g ai / ha</td><td></td><td></td>

<td>CHEAL</td><td> 88</td><td> 47</td><td> 100</td><td> 95</td><td> 5</td>

<td>POLAV</td><td> 90</td><td> 58</td><td> 99</td><td> 96</td><td> 3</td>

Additional field trials were conducted to evaluate weed control by early stage herbicides after emergence on oilseed rape and prior to emergence of weeds. Each trial was run as a standardized full block design with triplicate for each treatment on plot sizes from 2.5 x 5.0 m to 3.0 x 6.0 m.

In these trials, the herbicidal treatment included:

metazachlor at a dose of 750 g / ha clopyralid + picloram + aminopyralid at a dose of 60 + 20 + 10 g / ha metazachlor + clopyralid + picloram + aminopyralid at a dose of 750 + 60 + 20 + 10 g / ha

The herbicidal treatment was carried out by spraying the oilseed rape in the cotyledon phase post-emergence to 1 leaf, but pre-emergence spraying for any weeds.

Weed control rate was visually assessed and recorded 55 to 68 days after application as a percentage of weed control. Damage percentages represent overall plant damage due to all factors including: growth inhibition, developmental abnormalities, chlorosis, necrosis, growth inhibition, and other types of plant damage. Destruction is in the range of 0-100%, where 0 means no damage and 100 means complete failure.

Combinations of metazachlor in a mixture with clopyralid + picloram + aminopyralid have been found to show unexpected and unexpected synergistic effects in controlling VIOAR, PAPRH and GALAP, while metazachlor alone and the combination of clopyralid + picloram + aminopyralid alone do not give acceptable control of these species.

Table 3 below shows the results obtained in the above-described pre-emergence test for the combination of metazachlor with clopyralid + picloram + aminopyralide for VIOAR, PAPRH and GALAP. The results in Table 3 also show the expected weed control for the combinations of metazachlor with clopyralid + picloram + aminopyralid tested against VIOAR, PAPRH and GALAP, calculated according to the Colby method.

PL 217 747 B1

Table 3

Pre-emergence weed control

<td>Code of the weed according to Bayer</td><td>clopyralid + picloram + aminopyralid</td><td>metazachlor</td><td>metazachlor + clopyralid + picloram + aminopyralid</td><td>calculated according to Colby</td><td>difference</td>

<td></td><td>60 + 20 + 10g ai / ha</td><td>750 g ai / ha</td><td>750 + 60 + 20 + 10 g ai / ha</td><td></td><td></td>

<td>VIOAR</td><td> 40</td><td> 0</td><td> 67</td><td> 40</td><td> 27</td>

<td>PAPRH</td><td> 13</td><td> 10</td><td> 82</td><td> 22</td><td> 60</td>

<td>GALAP</td><td> 47</td><td> 53</td><td> 87</td><td> 75</td><td> 12</td>

The results of Tables 1, 2 and 3 show the synergistic herbicidal efficacy obtained with the compositions according to the invention.