WO2024224390A1

WO2024224390A1 - Synergistic herbicide mixture

Info

Publication number: WO2024224390A1
Application number: PCT/IL2024/050369
Authority: WO
Inventors: Andrew HORSFIELD
Original assignee: Adama Agan Ltd.
Priority date: 2023-04-24
Filing date: 2024-04-16
Publication date: 2024-10-31

Abstract

The invention includes a herbicide mixture of pyroxasulfone and linuron. The mixture can control weeds in both cropland and in other situations, and can control both susceptible weeds and weeds that have become herbicide resistant. The invention can be applied from prior to or after crop sowing and weed germination. The invention also describes a novel method of weed control with linuron and pyroxasulfone, where they are applied to the ground area prior to sowing and mechanically incorporated by the sowing process. This may optionally include a phytoene desaturase inhibitor herbicide.

Description

Synergistic herbicide mixture

Technical Field

The invention relates to novel herbicidal mixtures containing linuron and pyroxasulfone, which may optionally also include a Phytoene desaturase (PDS) inhibitor.

Background Art

The control of undesired vegetation is important to achieve crop productivity. In many cases, herbicides have an effect against a spectrum of weeds, but they do not control other types of weeds that are found in the cropping system to be protected. Therefore, there is a significant need to mix two or more herbicides.

Mixtures of selected herbicides have several advantages over the use of a single herbicide including (a) an increase in the spectrum of weeds controlled or an extension of weed control over a longer period of time, (b) an improvement in crop safety by using minimum doses of selected herbicides applied in combination rather than a single high dose of one herbicide, and (c) a delay in the appearance of resistant weed species to selected herbicides.

However, the activity and selectivity behaviour of any specific mixture is difficult to predict since the behaviour of each single herbicide in the mixture is often affected by the presence of the other(s) and the activity of the mixture may also vary considerably depending on chemical character, plant species, growth stage, and environmental conditions. Mostly, this practice results in reduced activity of the herbicides in the mixture.

Linuron and pyroxasulfone are herbicides used for both pre and early post -emergent control of weeds in cereals, soybeans, maize and a range of other crops. In prior art for pyroxasulfone, the combination with linuron is only described when used in combination with at least one additional herbicide and/or herbicide safener.

Linuron Linuron was first reported by K. Hartel (Meded. Landbouwhogesch. Opzoekingsstn. Staat Gent, 1962, 27, 1275).

Pyroxasulfone, having the chemical name 3-(5-(difluoromethoxy)-l-methyl-3- (trifluoromethyl)-l/7-pyrazol-4-yl]methanesulfonyl)-5,5-dimethyl-4,5-dihydro-l,2-oxazole, has the following structure:

Pyroxasulfone

Pyroxasulfone belongs to the class of 3-([(hetero)aryl]methanesulfonyl)-4,5-dihydro- 1,2-oxazoles and is used as an herbicide, in particular for pre-emergence control of annual grasses and some broad-leaved weeds in maize, soy beans, wheat and other crops. Pyroxasulfone's mode of action affects apical meristems and coleoptile development and inhibits the biosynthesis of very-long-chain fatty acids in plants with excellent herbicidal activity against grass and broadleaf weeds at lower application rates compared with other commercial herbicides. In fields of genetically modified crops, pyroxasulfone controlled weeds were resistant to non-selective herbicides. Pyroxasulfone has been classified in the Herbicide Resistance Action Committee Group K3.

Pyroxasulfone was first disclosed by Kumiai Chemical Industry Co., Ltd. and lhara Chemical Industry Co., Ltd. in WO 2002/062770. It is available on the marketplace as water dispersible granule and as a suspension concentrate.

Patent application JP2012025679A2 discloses mixtures of pyroxasulfone and safener dicyclonon. The application discloses that said mixture can also contain any other herbicidal active ingredients, providing a long list of possible candidates. Example 10 discloses a formulation comprising pyroxasulfone, dicyclonon, linuron and thiobencarb.

There is still a need to find better performing herbicides that improve the control of weeds, help in delaying resistance events and/or use less amounts of each herbicide, and in that way limiting phytotoxicity and environmental impact. Summary of the Invention

A first aspect is a herbicidal mixture comprising pyroxasulfone and linuron (mixture of the invention).

A second aspect is a formulation comprising the mixture of the invention and an agrochemically acceptable additive and/or carrier.

A third aspect is a method for controlling weed comprising applying to a locus an effective amount of the mixture of the invention or a tank mix or a formulation thereof.

A fourth aspect is the use of the mixture of the invention or a formulation thereof in a tank mixture.

A fifth aspect is a tank mix comprising the mixture of the invention or a formulation thereof.

The mixture of pyroxasulfone and linuron has proved to synergistically control weeds. Further, the addition of a third herbicide, such a PDS inhibitor, further increases the efficacy of the mixture.

Detailed Description of Preferred Embodiments

Definitions

Prior to setting forth the present subject matter in detail, it may be helpful to provide definitions of certain terms to be used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains.

As used herein, the phrase "agriculturally acceptable " means components which are known and accepted in the art for the formation of formulations for agricultural or horticultural use. Preferably, it refers to components accepted by a regulatory body for agricultural or horticultural use.

As used herein, the term "crop" includes reference to a whole plant, plant organ (e.g., leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, or plant seeds.

As used herein, the term "locus" includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also to areas under cultivation. As used herein, the term "mixture" refers, but is not limited to, a combination of two or more components in any physical form, e.g., blend, solution, alloy, or the like.

The term "a" or "an" as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms "a," "an" or "at least one" can be used interchangeably in this application.

For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In this regard, use of the term "about" herein specifically includes ±10% from the indicated values in the range. In addition, the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges.

Synergistic Herbicidal Mixture

According to one aspect, the present specification provides a herbicidal mixture comprising pyroxasulfone and linuron. In one embodiment, linuron and pyroxasulfone are the only active ingredients in the mixture, preferably the only herbicides. The inventors have found that the combination does not require the use of safeners, and thus the mixture of the invention preferably comprises no safeners, such as AD-67, benoxacor, BPCMS, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, jiecaowan, jiecaoxi, mefenpyr, mephenate, metcamifen, naphthalic anhydride, MG-191, dymron (daimuron), cumyluron, dimepiperate, or oxabetrinil.

In an alternative embodiment, the present mixtures may include additional active ingredients (also referred to as crop protection agents), whether or not the mixture comprises a safener, for example pesticides (herbicides, fungicides or insecticides) or agents for controlling phytopathogenic fungi or bacteria.

For example, the mixture may comprise at least one additional active ingredient, for example a herbicide, such as a PDS inhibitor, which can be one selected from the group consisting of beflubutamide, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon and picolinafen. For example, said PDS inhibitor is selected from the group consisting of phenyl-ethers, N-phenyl heterocycles and diphenyl heterocycles. Examples of phenyl-ether are beflubutamid, diflufenican and picolinafen. Examples of N-phenyl heterocycle are flurochloridone and norflurazon. Examples of diphenyl heterocycle are fluridone and flurtamone. In one embodiment the herbicidal mixture herein described comprises pyroxasulfone, linuron and beflubutamid. In a further embodiment the herbicidal mixture herein described comprises pyroxasulfone, linuron and diflufenican. In a further embodiment the herbicidal mixture herein described comprises pyroxasulfone, linuron and picolinafen.

Thus, another aspect of the invention is a formulation comprising a PDS inhibitor, such as one selected from the group consisting of phenyl-ethers, N-phenyl heterocycles and diphenyl heterocycles, preferably, diflufenican.

The formulations may comprise additional components, such as fertilisers and/or other plant nutritional compound, as well as systemic acquired resistance compound (for example, trimethyl glycine, acibenzolar-s-methyl, probenazole, isotianil, tiadinil, laminarin, extract from Reynoutria sachalinensis, Bacillus mycoides (isolate J), cell walls of Saccharomyces cerevisiae LAS117, fosetyl-al, phosphorus acid, diclobentiazox, peptides.

The present formulations can be used as prepared or diluted before applying into the field (tank mixture), which is one aspect of the invention. The present formulations can also be concentrated compositions, or so-called "ready-to-use" formulations, that is to say, formulations ready for use. The present formulations may be employed or prepared in any conventional form, for example, in the form of a formulation or a twin pack, as emulsion concentrates (EC), microemulsion concentrates (MEC), suspension concentrates (SC), soluble concentrates (SL), suspoemulsion (SE), oil dispersions (OD), water dispersible granules (WDG), water soluble granules (SG), or wettable powders (WP). Thus, for example, the formulation containing linuron and pyroxasulfone can be a capsule suspension, dispersible concentrate, emulsifiable concentrate, emulsifiable granule, emulsifiable powder, granule, micro- emulsion, oil dispersion, oil in water emulsion, oil miscible liquid, soluble concentrate, suspension concentrate, suspo-emulsion, water dispersible granule, water soluble powder, ultra-low volume liquid, water soluble tablet, wettable power or a mixed formulation such as a capsule suspension and suspension concentrate.

The present invention provides a formulation comprising a mixture of pyroxasulfone and linuron and an agrochemically acceptable additive and/or carrier, preferably containing no safener. Such formulations can be formulated using agriculturally acceptable carriers, surfactants or other application promoting adjuvants customarily employed in formulation technology and formulation techniques that are known in the art. In an embodiment, the amount of active ingredients in the formulation can be about 0.1-99 wt. %, about 0.1-95 wt. %, or about 0.1-90 wt. %, based on the total weight of the formulation. For example, the amount of active ingredients in the formulation can be about 1-80 wt %, based on the total weight of the formulation. In another embodiment, the amount of active ingredients in the formulation is about 5-90 wt %, based on the total weight of the formulation, for example, about 10 to 85 wt %, about 20 to 80 wt %, about 30 to 80 wt %, about 40 to 80 wt %, about 35 to 70 wt % or about 50 to 90 wt %, based on the total weight of the formulation.

Examples of suitable liquid carriers potentially useful in the present formulations include but are not limited to water; aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes; alcohols such as methanol, cyclohexanol, and decanol; ethylene glycol; polypropylene glycol; dipropropylene glycol; N,N dimethylformamide; dimethylsulfoxide; N- alkylpyrrolidones such as N-methyl-2-pyrrolidone; paraffins; various oils such as olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed, or coconut oil; fatty acid esters; ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4- methyl-2-pentanone; and the like.

Examples of suitable solid carriers potentially useful in the present formulations include but are not limited to mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, less, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, sodium carbonate and bicarbonate, and sodium sulfate; ground synthetic materials; fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal, and nutshell meal; cellulose powders; and other solid carriers. As used herein, the term "surfactant" refers to any agriculturally acceptable material which imparts emulsifiability, stability, spreading, wetting, dispersibility, or other surfacemodifying properties. Examples of suitable surfactants include, but are not limited to, nonionic, anionic, cationic and ampholytic types such as alkoxylated fatty alcohols, ethoxylated polysorbate (e.g. tween 20), ethoxylated castor oil, lignin sulfonates, fatty acid sulfonates (e.g. lauryl sulfonate), phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styrylphenol ethoxylates, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, alkylarylsulfonates, ethoxylated alkylphenols and aryl phenols, polyalkylene glycols and sorbitol esters.

Other ingredients, such as adjuvants, wetting agents, anti-foaming, adhesives, neutralizers, thickeners, binders, sequestrates, spreaders, wetters or anti-freeze agents, may also be added to the present formulations.

The present invention provides a method of controlling undesired vegetation comprising applying to a locus of the undesired vegetation a herbicidal effective amount of a mixture comprising pyroxasulfone and linuron.

The present invention provides a herbicidal mixture comprising pyroxasulfone and linuron, which preferably displays a synergistic control of weeds.

The present invention provides herbicidal mixture comprising pyroxasulfone and linuron, preferably, wherein the weight ratio between pyroxasulfone and linuron is between 2:1 and 1:250, for example, between 1:1 and 1:200, or between 1:1 and 1:20 or between 1:1 and 15, for example between 1:1.6 and 1:40, for example, between 1:1 to 1:10, or between 1:2 to 1:8. Alternatively, the weight ratio between pyroxasulfone and linuron can be between 1:10 and 1:50, or between more than 1:12 and 1:50, for example between 1:15 and 1:45.

Pyroxasulfone can be applied in different rates, depending on the weather conditions, the weed, the crop and other factors. Since the mixture of the invention shows synergy, the amount of pyroxasulfone added can be less than that that would be needed if pyroxasulfone was the only active ingredient. For example, pyroxasulfone is applied at a rate of about 1 g ai/ha to about 240 g ai/ha, for example, about 5 g ai/ha to about 150 g ai/ha, about 10 g ai/ha to about 120 g ai/ha, about 10 g ai/ha to about 100 g ai/ha.

Linuron can be applied in different rates, depending on the weather conditions, the weed, the crop and other factors. Since the mixture of the invention shows synergy, the amount of linuron added can be less than that that would be needed if linuron was the only active ingredient. For example, linuron is applied at a rate of about 1 g ai/ha to about 3000 g ai/ha, for example, about 10 g ai/ha to about 2000 g ai/ha, about 50 g ai/ha to about 1000 g ai/ha, about 100 g ai/ha to about 800 g ai/ha.

The present invention provides a method of controlling undesired vegetation comprising applying to a locus of the undesired vegetation a her bicida I ly effective amount of a synergistic mixture of the first aspect, or a formulation or tank mix thereof.

The present invention provides a method of controlling weeds that have become herbicide-resistant, for example, resistant to herbicides that inhibit Very Long Chain Fatty Acids (VLCFAs herbicide), such as at least one VLCFA herbicide selected from the group consisting of alpha-chloroacetamides, alpha-thioacetamides, alpha-oxyacetamides, oxiranes, isoxazolines, benzofuranes and thiocarbamates. It is preferred that the VLCFA herbicide is an isoxazoline selected from fenoxasulfone and pyroxasulfone, preferably, pyroxasulfone. It has become apparent to the inventors the linuron can be surprisingly used for controlling weeds that are resistant to herbicides that inhibit Very Long Chain Fatty Acids (VLCFAs herbicide), wherein linuron and the VLCFA herbicide are used in combination, and linuron is added at a rate (grams of linuron per hectare) that would not control the weed (e.g. below 10% control) if linuron was added without the herbicide that adds VLCFAs. That is, it has been found that it is possible to revert weed resistance to VLCFA herbicides, when such herbicides are used in combination with linuron, whether this involves adding the VLCFA herbicides at the same time as linuron, or adding both sequentially.

The combination of pyroxasulfone and linuron provides greater herbicidal activity on weed species that have become herbicide resistant such as, but not limited to, Lolium rigidum, compared with the solo components.

In an embodiment, the mixture is applied on crops or on non-crop areas. The mixture can be applied, for example, in cereals, such as, wheat (e.g. winter wheat or spring wheat), barley (e.g. winter barley or spring barley), triticale, cereal rye, fodder cereals, or maize, cotton, bananas, fallow land, chickpeas, field peas, lentils, lupins, peanuts, soybeans, sugarcane, sunflower, non-crop areas, such as turfgrass and grassland. That is, the locus of undesired vegetation may contain one or more of these crops.

In yet another embodiment, the undesired vegetation may include one or more of ryegrass (Lolium rigidum), wild oats (Avena spp), Avena fatua, Phalaris spp., Vulpia spp., Argemone Mexicana and Raphanus raphanistrum.

In an embodiment, the herbicidal mixture is applied to the locus of undesired vegetation in an amount, or at a rate of application, of from 0.01 to 100 liter/ha. In yet another embodiment, the herbicidal mixture is applied in an amount of from 0.1 to 10 liter/ha. In another embodiment, the herbicidal mixture is applied in an amount of from 0.1 to 1 liter/ha. In a specific embodiment, the mixture is applied to the locus of undesired vegetation in an amount of 0.1 liter/ha. In yet another specific embodiment, the mixture is applied in an amount of 0.25 liter/ha. In still another specific embodiment, the mixture is applied in an amount of 0.5 liter/ha. In still yet another specific embodiment, 20 the mixture is applied in an amount of 0.75 liter/ha. In a further specific embodiment, the mixture is applied in an amount of 2 liter/ha. In yet another specific embodiment, the mixture is applied in an amount of 1 liter/ha.

In another embodiment, the herbicidal mixture is applied to the locus of undesired vegetation in an amount of from 1 to 2000 g ai/ha. In a further embodiment, the herbicidal mixture is applied in an amount of from 100 to 1000 g ai/ha.

In another embodiment, the present subject matter provides a kit comprising the herbicidal mixture as described herein, or components thereof. Such kits may comprise, in addition to the aforementioned active components, one or more additional active and/or inactive ingredients, either within the provided herbicidal formulation or separately. Certain kits comprise pyroxasulfone and linuron, and/or a combination thereof, each in a separate container, and each optionally combined with a carrier. In an embodiment, the kit comprises pyroxasulfone and linuron.

Linuron and pyroxasulfone can be added simultaneously as a ready-mix formulation or tank mixture, or can be added sequentially. The mixture of linuron and pyroxasulfone is preferably added from prior to sowing a crop and prior to germination of undesired vegetation, to after sowing and/or emergence of a crop and weeds.

In yet another aspect the present invention provides a method for controlling weeds with linuron and pyroxasulfone including the steps of: applying a formulation containing linuron to a ground area intended for growing a crop; and mechanically incorporating the formulation into the ground area at the same time as sowing the crop wherein pyroxasulfone is added at any time, preferably pre-emergent, more preferably, pre-sowing, or post-sowing and prior to crop and weed emergence, or early post crop and weed emergence, together with or separately from linuron. In a preferred embodiment, pyroxasulfone is added at the time as linuron.

A synergistic effect exists wherever the action of a combination of active components is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount (or an effective amount of a synergistic formulation or combination) as discussed herein is an amount that exhibits greater pesticidal activity than the sum expected from the pesticidal activities of the individual components.

In the context of the present subject matter, the term "synergy" is as defined by Colby S. R. in an article entitled "Calculation of the synergistic and antagonistic responses of herbicide combinations" published in the journal Weeds, 1967, 15, p. 20-22, incorporated herein by reference in its entirety. The action expected for a given combination of three active components can be calculated as follows:

E = X + Y- (X * F/ 100)

Where

X = effect in percent using active compound A at an application rate a;

Y = effect in percent using active compound B at an application rate b;

E = expected effect (in %) of A + B at application rates a + b.

If the value calculated in this manner is higher than the value E calculated according to Colby, a synergistic effect is present. When the percentage of control observed for the combination is equal to the expected percentage, there is an additive effect and wherein the percentage of herbicidal control observed for the combination is lower than the expected percentage, there is an antagonistic effect.

Clauses

Clause 1. A herbicidal mixture comprising pyroxasulfone and linuron.

Clause 2. The herbicidal mixture according to clause 1, wherein the weight ratio pyroxasulfone:linuron is from 2:1 to 1:250.

Clause 3. The herbicidal mixture of any one of clauses 1 to 2, said mixture showing a synergistic control over weeds.

Clause 4. The herbicidal mixture of any one of clauses 1 to 3, wherein pyroxasulfone is applied at a rate of about 12.5 g ai/ha to about 240 g ai/ha.

Clause 5. The herbicidal mixture of any one of clauses 1 to 4, wherein linuron is applied at a rate of about 37.5 g ai/ha to about 3000 g ai/ha.

Clause 6. The herbicidal mixture of any one of the previous clauses, wherein the mixture comprises no safener.

Clause 7. The herbicidal mixture of any one of the previous clauses, wherein linuron and pyroxasulfone are the only active ingredients.

Clause 8. The herbicidal mixture according to any of clauses 1 to 5 further comprises at least one additional active ingredient.

Clause 9. The herbicidal mixture according to clause 6 further comprises at least one additional active ingredient.

Clause 10. The herbicidal mixture of clause 8 or 9, wherein said additional active ingredient is a PDS inhibitor.

Clause 11. The herbicidal mixture of clause 10, wherein said PDS inhibitor is selected from the group consisting of beflubutamide, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon and picolinafen.

Clause 12. The herbicidal mixture of clause 10, wherein said PDS inhibitor is selected from the group consisting of phenyl-ethers, N-phenyl heterocycles and diphenyl heterocycles. Clause 13. The herbicidal mixture of clause 12, wherein said phenyl-ether is selected from the group consisting of beflubutamid, diflufenican and picolinafen.

Clause 14. The herbicidal mixture of clause 12, wherein said N-phenyl heterocycle is flurochloridone or norflurazon.

Clause 15. The herbicidal mixture of clause 12, wherein said diphenyl heterocycle is fluridone or flurtamone.

Clause 16. The herbicidal mixture of clause 1 or 13, comprising pyroxasulfone, linuron and diflufenican.

Clause 17. The herbicidal mixture according to any of clauses 1 to 16 comprising a herbicide safener applied as either a foliar, soil or seed treatment application.

Clause 18. The herbicidal mixture according to any of clauses 1 to 17 comprising a fertiliser and/or other plant nutritional compound.

Clause 19. The herbicidal mixture according to any of clauses 1 to 18 comprising a systemic acquired resistance compound.

Clause 20. A formulation comprising the mixture defined in any of clauses 1 to 19.

Clause 21. The formulation according to clause 20 comprising one or more of the group consisting of adjuvants, wetting agents, anti-foaming agents, adhesives, neutralizers, thickeners, binders, sequestrates, spreaders, wetters and anti-freeze agents.

Clause 22. The formulation according to any of clauses 20 and 21 that is a capsule suspension, dispersible concentrate, emulsifiable concentrate, emulsifiable granule, emulsifiable powder, granule, micro-emulsion, oil dispersion, oil in water emulsion, oil miscible liquid, soluble concentrate, suspension concentrate, suspo-emulsion, water dispersible granule, water soluble powder, ultra-low volume liquid, water soluble tablet, wettable power or a mixed formulation such as a capsule suspension and suspension concentrate.

Clause 23. A tank mix comprising a mixture as defined in any of clauses 1 to 19 or the formulation as defined in any of clauses 20 to 22.

Clause 24. A method for controlling weed comprising applying to a locus an effective amount of a mixture as defined in any of clauses 1 to 19, a formulation as defined in any of clauses 20 to 22 or a tank mixture as defined in clause 23. Clause 25. The method of clause 24, wherein said locus is a field of crop.

Clause 26. The method of clause 25, wherein the crop is selected from the group consisting of wheat, barley, triticale, cereal rye, fodder cereals, maize, cotton, bananas, fallow land, chickpeas, field peas, lentils, lupins, peanuts, soybeans, sugarcane, and sunflower.

Clause 27. The method according to any of clauses 24 to 26, wherein the weed is selected from annual ryegrass (Lolium rigidum) and/or wild oats (Avena spp).

Clause 28. The method according to any of clauses 24 to 27 comprising adding linuron and/or pyroxasulfone from prior to sowing a crop and prior to germination of undesired vegetation, to after sowing and/or emergence of a crop and weeds.

Clause 29. The method for controlling weeds with linuron and pyroxasulfone according to any of clauses 24 to 28 that comprises: i. applying a composition comprising linuron to a ground area intended forgrowing a crop; and ii. mechanically incorporating the composition into the ground area at the same time as sowing the crop wherein pyroxasulfone is added at any time.

Clause 30. The method according to Clause 29, wherein pyroxasulfone is added pre-emergent, preferably, pre-sowing, or post-sowing and prior to crop and weed emergence, or early post crop and weed emergence, together with or separately from linuron.

Clause 31. The method according to Clause 29, wherein pyroxasulfone is added at the same time as linuron.

Clause 32. The method according to any of clauses 29 to 31, wherein the weed is herbicideresistant.

Clause 33. The method of clause 32, wherein the weed is resistant herbicides that inhibit Very Long Chain Fatty Acids (VLCFAs herbicide).

Clause 34. The method of clause 33, wherein the weed is resistant to at least one VLCFA herbicide selected from the group consisting of alpha-chloroacetamides, alpha- thioacetamides, alpha-oxyacetamides, oxiranes, isoxazolines, benzofuranes and thiocarbamates.

Clause 35. The method of clause 34, wherein the weed is resistant to an isoxazoline selected from fenoxasulfone and pyroxasulfone.

Clause 36. The method of clause 35, wherein the weed is resistant to pyroxasulfone.

Clause 37. Use of linuron for controlling weeds that are resistant to herbicides that inhibit Very Long Chain Fatty Acids (VLCFAs herbicide), wherein linuron and a VLCFA herbicide are used in combination, and linuron is added at a rate (grams of linuron per hectare) that would not control the weed if linuron was added without any other herbicide.

Clause 38. Use of the mixture according to any of clauses 1 to 9 or a formulation according to any of clauses 20 to 22 in a tank mix.

Detailed Description of Some Embodiments

In the examples below, unless otherwise stated, the following materials were used:

Novali is available from Adama Australia Pty Ltd, Suite 1, Level 4, Building B, 207 Pacific Highway, St Leonards NSW 2065, Australia.

Linurex is available from Adama Australia Pty Ltd, Suite 1, Level 4, Building B, 207 Pacific Highway, St Leonards NSW 2065, Australia.

Bonanza Elite is available from Adama Australia Pty Ltd, Suite 1, Level 4, Building B, 207 Pacific Highway, St Leonards NSW 2065, Australia. Experimental details

Example 1

In this example, a field trial was conducted in 2021 at Owen, South Australia, Australia in a crop of wheat cv. Vixen. Pyroxasulfone, linuron and pyroxasulfone + linuron herbicide treatments were applied post crop-emergence targeting emerged annual ryegrass (Lolium rigidum) at the four leaf to one tiller growth stage (Table 1). The herbicides, alone or in a mixture as set out in Tables, was applied by spraying in a volume of 100 L/ha.

An assessment of control of annual ryegrass plants was conducted 58 days after application and annual ryegrass panicles 73 days after application (DAA) as per Table 2 below.

The results established that:

The combination of pyroxasulfone and linuron was synergistic in controlling annual ryegrass.

Example 2

In this example, a field trial was conducted in 2021 at York, Western Australia, Australia in a crop of wheat cv. Scepter. Pyroxasulfone, linuron and pyroxasulfone and linuron tank mix herbicide treatments were applied post crop-emergence targeting emerged wild oats (Avena fatua) at the one to three leaf stage (Table 2). The herbicides, alone or in a mixture as set out in Table 2, was applied by spraying in a volume of 100 L/ha.

An assessment of control of wild oats plants was conducted 54 days after application and percent reduction in panicles 90 days after application (DAA) as per Table 2 below.

The results established that:

The combination of pyroxasulfone and linuron was synergistic in controlling wild oats.

Example 3

In this example, a pot trial was conducted in 2021 at the University of Adelaide, South Australia, Australia. Pyroxasulfone, linuron and pyroxasulfone + linuron herbicide treatments were applied pre-emergence to pots containing Susceptible annual ryegrass (Lolium rigidum) (Table 3). Fifty seeds of each weed type were added to four replicate pots containing cocoa peat and sand potting mix, then covered with 5 mm of soil, then sprayed and covered with a further 5 mm soil to simulate incorporate by sowing application. The herbicides, alone or in a mixture as set out in Table 3, was applied by spraying in a volume of 100 L/ha in a spray chamber.

Assessment of percent biomass reduction and percent weed control were conducted

28 days after application.

Table 3: Percent of biomass reduction in Susceptible Annual ryegrass

The results established that the combination of pyroxasulfone and linuron was synergistic in reducing the biomass of susceptible annual ryegrass. In all cases marked with an asterisk (*) pyroxasulfone and/or linuron individually already achieved a very high control percentage, and therefore synergy was impossible to assess. These results however confirm that no antagonism was observed between both active ingredients.

Example 4

An analogous experiment to Example 3 was done for EP162 (low level resistance to pyroxasulfone) annual ryegrass (Lolium rigidum) (Table 4).

Table 4: Percent of biomass reduction in EP162 Annual ryegrass

The results established that the combination of pyroxasulfone and linuron was synergistic in reducing the biomass of EP162 annual ryegrass. In all cases marked with an asterisk (*) pyroxasulfone and/or linuron individually already achieved a very high control percentage, and therefore synergy was impossible to assess. These results however confirm that no antagonism was observed between both active ingredients.

Example 5

An analogous experiment to Example 3 was done for 198-15 (intermediate resistance to pyroxasulfone) annual ryegrass (Lolium rigidum) (Table 5).

Table 5: Percent of biomass reduction in 198-15 Annual ryegrass

The results established that the combination of pyroxasulfone and linuron was synergistic in reducing the biomass of 198-15 annual ryegrass. In all cases marked with an asterisk (*) pyroxasulfone and/or linuron individually already achieved a very high control percentage, and therefore synergy was impossible to assess. These results however confirm that no antagonism was observed between both active ingredients.

Example 6 An analogous experiment to Example 3 was done for wild oats (Avena fatua) (Table

6). Table 6: Percent of biomass reduction in wild oats

t Synergy confirmed, but Colby value could not be calculated as expected control was 0

The results established that the combination of pyroxasulfone and linuron was synergistic in reducing the biomass of wild oats. In all cases marked with an asterisk (*) pyroxasulfone and/or linuron individually already achieved a very high control percentage, and therefore synergy was impossible to assess. These results however confirm that no antagonism was observed between both active ingredients.

Example 7

In this example, a trial similar to that described in Example 3 was performed, but measuring weed control instead of biomass reduction. Results are shown in Table 7.

The results established that the combination of pyroxasulfone and linuron was synergistic in weed control for all weeds tested. Only in two treatments the mixture displayed an additive behavior: P+L (75+250) in EP162 and 198-15. In all cases marked with an asterisk (*) pyroxasulfone and/or linuron individually already achieved a very high control percentage, and therefore synergy was impossible to assess. These results however confirm that no antagonism was observed between both active ingredients.

Example 8

In this example, a pot trial was conducted in 2022 at the University of Adelaide, South Australia, Australia. Pyroxasulfone, linuron and diflufenican herbicide treatments were applied pre-emergence to pots containing either annual ryegrass (Lolium rigidum) biotype EP162 with low level resistance to pyroxasulfone, wild oats (Avena fatua) or wild radish (Raphanus raphanistrum) (Table 8). Seeds of each weed type were added to four replicate pots containing cocoa peat and sand potting mix, then covered with 5 mm of soil, then sprayed and covered with a further 5 mm soil to simulate incorporate by sowing application. The herbicides, alone or in a mixture as set out in Table 7, were applied by spraying in a volume of 100 L/ha in a spray chamber.

Assessment of percent weed control was conducted 28 days after application.

The results established that:

The combination of pyroxasulfone, linuron and diflufenican was synergistic on annual ryegrass and wild oats when applied at ratios of 1:10:0.5 to 2:10:1;

The combination of pyroxasulfone, linuron and diflufenican was synergistic on wild radish when applied at ratios of 2:20:1, 1:20:2 and 2:5:1.

Table 8: Percent weed control

The results established that the combination of pyroxasulfone, linuron and diflufenican was synergistic in weed control for all weeds tested. Only in one treatment the mixture displayed an additive behavior: P+L+D (12.5+250+12.5) in Wild Oats.

Claims

1. A herbicidal mixture comprising pyroxasulfone and linuron.

2. The herbicidal mixture of claim 1, wherein the weight ratio pyroxasulfone:linuron is from 2:1 to 1:250.

3. The herbicidal mixture of any one of claims I to 2, said mixture showing a synergistic control over weeds.

4. The herbicidal mixture of any one of the previous claims, wherein the mixture comprises no safener.

5. The herbicidal mixture of any one of the previous claims, wherein linuron and pyroxasulfone are the only active ingredients.

6. The herbicidal mixture of any one of claims 1 to 3 further comprising at least one additional active ingredient.

7. The herbicidal mixture of claim 4 further comprising at least one additional active ingredient.

8. The herbicidal mixture of claim 6 or of claim 7, wherein said additional active ingredient is a PDS inhibitor.

9. The herbicidal mixture of claim 8, wherein said PDS inhibitor is selected from the group consisting of beflubutamide, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon and picolinafen.

10. The herbicidal mixture of claim 9, comprising pyroxasulfone, linuron and diflufenican.

11. A formulation comprising a mixture as defined in any of claim 1 to 10 and an agrochemically acceptable additive and/or carrier.

12. The formulation of claim 11 comprising one or more of the group consisting of adjuvants, wetting agents, anti-foaming agents, adhesives, neutralizers, thickeners, binders, sequestrates, spreaders, wetters and anti-freeze agents.

13. A tank mix comprising a mixture as defined in any of claims 1 to 10 or the formulation as defined in any of claims 11 or 12.

14. A method for controlling weed comprising applying to a locus an effective amount of a mixture as defined in any of claims 1 to 10 or a formulation as defined in claims 11 or 12 or a tan mix as defined in claim 13.

15. The method of claim 14 comprising the steps of: applying a formulation containing linuron to a ground area intended for growing a crop; and mechanically incorporating the formulation into the ground area at the same time as sowing the crop wherein pyroxasulfone is added at any time, preferably at the same time as linuron.

16. The method of any one of claims 14 or 15, wherein the weed is selected from annual ryegrass (Lolium rigidum) and/or wild oats (Avena spp).

17. The method of anyone of claims 14 to 16, wherein the weed has become resistant to at least one herbicide.

18. The method of claim 17, wherein said weed has become resistant to a VLCFA inhibiting herbicide.

19. Use of the mixture as defined in any of claims 1 to 10 or the formulation as defined in claims 11 or 12 in a tank mix.