WO2019034934A1

WO2019034934A1 - Oil dispersable formulation

Info

Publication number: WO2019034934A1
Application number: PCT/IB2018/001019
Authority: WO
Inventors: Vladimir GUBRIY; Shlomo WINDREICH
Original assignee: Adama Agan Ltd.
Priority date: 2017-08-14
Filing date: 2018-08-13
Publication date: 2019-02-21
Also published as: CN110996660A

Abstract

The present invention provides a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet, an amount of at least one sulfonylurea herbicide, and an agrochemically acceptable non-aqueous liquid carrier, wherein the flufenacet is dissolved in the non-aqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier. The subject application also provides methods for controlling weeds comprising applying the stable formulations described herein and processes for preparing the stable formulations described herein.

Description

OIL DISPE SABLE FORMULATION

This application claims priority of U.S. Provisional Application No. 62/545,351, filed August 14, 2017, the contents of which are hereby incorporated by reference.

Throughout this application, various publications are referenced, including referenced in parenthesis. The disclosures of all referenced 10 publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains .

The present subject matter relates to pesticidal compositions for use in agricultural pest control applications. In particular, this subject matter provides a stable herbicidal liquid formulation comprising flufenacet and at least one sulfonylurea herbicide. BACKGROUND

Sulfonylureas and oxyacetamides , including flufenacet, are generally known to have herbicidal activity.

Sulfonylurea herbicides are acetolactate synthase (ALS) or acetohydroxyacid synthase (AHAS) inhibitors. They act by inhibiting biosynthesis of branched-chain amino acids, such as valine and isoleucine, thereby inhibiting cell division and plant growth.

Oxyacetamide herbicides, including flufenacet, inhibit fatty acid metabolism thereby also inhibiting cell division and plant growth .

Applying two active ingredients with two different modes of action has many advantages such as reduced rate of application, reduced number of application and, in some cases, a synergistic effect wherein the efficacy is increased. Combining different active ingredients has the added value of preventing the emergence of resistant species.

However, when each active ingredient is in its own formulation, there are often incompatibility issues when the formulations are tank-mixed in order to combine active ingredients for the application in the field.

Combining two active ingredients into one formulation can be challenging due the variance in structure of the active ingredients, especially when one or both active ingredients are highly unstable.

Flufenacet, an oxyacetamide herbicide, is a highly sensitive molecule which rapidly decomposes in various conditions.

N-isomer of flufenacet which is less active and/or more toxic, is one of the decomposition products of flufenacet. Sulfonylurea herbicides and oxyacetamide herbicides are each formulated as solid and liquid formulations in presence of stabilizing agents such as pH adjuster.

Sulfonylurea herbicides are sensitive to acidic conditions and hydrolyzed rapidly in aqueous and/or acid environment. Sulfonylurea herbicides can be stable at pH values above 7.

Flufenacet, on the other hand, is not stable in neutral or basic conditions. In neutral or basic conditions, isomerization of the molecule takes place causing rapid formation and accumulation of N-isomers . In the prior art, flufenacet is formulated as a solid composition and stabilized with acid. EP922388B discloses solid dry compositions where the flufenacet is stabilized by adding an amount of citric acid to reduce the pH of the composition and thus preventing the formation of N-isomer. In foliar application, liquid formulations are preferred due to the advantage of better miscibility which reduces problems of flowability . Accordingly, the problem to be solved by the subject invention is to combine sulfonylurea and flufenacet into a single stable liquid formulation. Disclosed herein are stable liquid formulations comprising both sulfonylurea herbicide (s) and flufenacet.

SUMMARY

The present invention provides a stable herbicidal non-aqueous liquid formulation comprising: a) an amount of flufenacet;

b) an amount of at least one sulfonylurea herbicide; and c) an agrochemically acceptable non-aqueous liquid carrier, wherein the flufenacet is dissolved in the non-aqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier. The subject application also provides a method for controlling weeds comprising applying the stable herbicidal non-aqueous liquid formulation described herein to a weed, a portion of a weed, an area or soil adjacent to a weed, and/or a seed of a weed so as to thereby control the weeds. The subject application also provides a method of controlling weed comprising: a) obtaining a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet, an amount of at least one sulfonylurea herbicide; and an agrochemically acceptable non-aqueous liquid carrier, wherein in the flufenacet is dissolved in the non-aqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier, and b) applying the stable herbicidal formulation to a weed, a portion of a weed, an area or soil adjacent to a weed, and/or a seed of a weed so as to thereby control the weed.

The present invention also provides a process for preparing the stable herbicidal non-aqueous liquid formulation described herein, wherein the method comprises the steps of:

(i) dissolving the flufenacet in the non-aqueous carrier to form a solution; adding the sulfonamide herbicide to the solution of step (i) to form a suspension; and

milling the suspension to obtain the stable formulation.

DETAILED DESCRIPTION

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. The following definitions are provided for clarity.

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

N

in this application.

As used herein, the term "about" when used in connection with a numerical value includes ±10% from the indicated value. In addition, 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. It is understood that where a parameter range is provided, all integers within that range, and tenths thereof, are also provided by the invention. For example, "0.1-80%" includes 0.1%, 0.2%, 0.3%, etc. up to 80%. As used herein, the term "pesticide" broadly refers to an agent that can be used to control and/or kill a pest. The term is understood to include but is not limited to fungicides, insecticides, nematicides, herbicides, acaricides, parasiticides or other control agents. For chemical classes and applications, as well as specific compounds of each class, see "The Pesticide Manual Thirteenth Edition" (British Crop Protection Council, Hampshire, UK, 2003) , as well as "The e- Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, UK, 2003-04), the contents of each of which are incorporated herein by reference in their entirety. As used herein, the term "weed" includes any undesired vegetation.

As used herein, the term "plant" or "crop" includes reference to whole plants, plant organs (e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, or plant seeds. This term also encompasses plant crops such as fruits. In yet another embodiment, the term "plant" may include the propagation material thereof, which may include all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant. This includes seeds, tubers, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. As used herein, the term "locus" includes not only areas where pests, including weeds, may already be growing, but also areas where pests, including weeds, have yet to emerge, and also to areas under cultivation.

As used herein, the term "mixture" or "combination" refers, but is not limited to, a combination in any physical form, e.g., blend, solution, alloy, or the like.

As used herein, the term "effective amount" refers to an amount of the compound that, when ingested, contacted with or sensed, is sufficient to achieve a good level of control. As used herein, the phrase "agrochemically acceptable carrier" means carriers which are known and accepted in the art for the formation of formulations for agricultural or horticultural use.

As used herein, the term "adjuvant" is broadly defined as any substance that itself is not an active ingredient but which enhances or is intended to enhance the effectiveness of the active ingredient with which it is used. Adjuvants may be understood to include, spreading agents, penetrants, compatibility agents, and drift retardants. As used herein, the term "additive" is defined as any substance that is not an active ingredient but is added to the formulation such as sticking agents, surfactants, synergists, buffers, acidifiers, defoaming agents and thickeners. As used herein, an "ultra-low naphthalene solvent" is a solvent with a naphthalene concentration of less than 0.1 wt %.

As used herein, a "low naphthalene solvent" is a solvent with a naphthalene concentration of less than 1 wt % .

As used herein, the term "stable" when used in connection with a formulation means that no significant decomposition of the active ingredients in the formulation is observable after at least 7 days of storage at a temperature of at least 20°C. For example, no significant amount of flufenacet N-isomer will form after at least 7 days of storage at a temperature of at least 20°C.

U.S. Patent No. 6,479,432 disclosed a liquid suspension formulation comprising one or more herbicidally active compounds from the group of the sulfonylureas in suspended form and one or more active compounds which are partially or completely dissolved in the formulation. However, due to the unique chemical properties of flufenacet, preparing the formulation as taught by U.S. Patent No. 6, 479,432 using sul fonylurea ( s ) and flufenacet will not result in a formulation that is stable as defined above.

As used herein, the term "tank mix" means that two or more chemical pesticides or formulations are mixed in the spray tank at the time of spray application.

As used herein, the term "safener" refers to an agent that increase the tolerance of plants to herbicides without significantly affecting the effectiveness of the active ingredients .

As used herein, the term "thickener" refers to an agent that increase the viscosity of a liquid formulation without substantially changing other properties of the formulation. As used herein, the term "non-aqueous" when used to describe an agrochemically acceptable carrier or a formulation means that the agrochemically acceptable carrier or the formulation is substantially free of water.

Water vapor is one of the most abundant atmospheric gases. Some chemical compounds and formulations tend absorb moisture when they are exposed to the water in the atmosphere. The amount and rate of absorption depends on a variety of factors such as the hygroscopic properties of the chemical compound or formulation, atmospheric conditions (ex. humidity) and duration of exposure. Some chemical compounds and formulations also tend to absorb water from other ingredients/components in the formulation. Accordingly, the agrochemically acceptable carriers and formulations of the subject invention may contain slight amounts of water, but they should be deemed "non-aqueous" as long as no water was affirmatively added to the agrochemically acceptable carrier or the formulation.

The amount of water absorbed into a compound or a formulation may be measured using a number of techniques including Karl Fischer titration.

Non-aqueous liquid formulations

Agrochemical oil dispersions (OD) are stable suspensions of agrochemical active ingredients, such as pesticides and crop protection chemicals, in non-aqueous fluids, which may contain other dissolved active ingredients. Oil dispersions are particularly useful for formulating organic, ^' insoluble, and solid active ingredients.

Oil dispersion formulations are concentrated non-aqueous liquid formulations which are diluted with water before use to produce an aqueous composition which is - used in crop protection. To enable dispersion in water, such formulations contain emulsifiers, dispersants and further formulation components such as thickeners, antifoaming agents and solid carriers. Oil dispersions are often chosen if the active ingredient is sensitive to water or if the oil is required to act as an adjuvant in order to improve biological performance of the pesticide. Oil dispersions are usually free of water. This is to prevent degradation of active ingredients and/or phase separation of the formulation .

Oil dispersion formulations provide certain advantages to the farmer. Active ingredients which are usually unstable in water may now be formulated in solid suspended form. Oil-based adjuvants may also be combined with these types of formulations in order to enhance efficacy. Further, suspension of active ingredients in non-aqueous liquid carrier can possibly lead to formulations with higher concentration of active ingredient than would otherwise be possible. This is because active ingredients have a solubility limit on the amount that can be added into a formulation .

In addition, the non-aqueous liquid formulation may include an adjuvant and/or safener therein, as opposed to adding the adjuvant and/or safener in the spray tank. This further brings logistic, packaging and storage benefits to the farmer, as a single product can be used instead of two or more.

The non-aqueous liquid formulation of the present invention comprising flufenacet and at least one sulfonylurea herbicide was found to be stable and no decomposition products of flufenacet were formed, when the formulation was stored at various conditions and for various durations. Moreover, a major advantage of this formulation is its ability to suspend at least one sulfonylurea herbicide in non-aqueous liquid carrier and dissolve flufenacet without loss of stability of the formulation. This allows active ingredients with different physicochemical properties commonly formulated into separate formulations, such as emulsifiable concentrate (EC) formulation, suspenpension concentrate (SC) and water dispersible granule (WG) formulation, to be combined into a single formulation.

b) an amount of at least one sulfunylurea herbicide; and c) an agrochemically acceptable non-aqueous liquid carrier, wherein the flufenacet is dissolved in the non-aqueous liquid carrier and the sulfunylurea herbicide is suspended in the non-aqueous liquid carrier.

In some embodiments, the sulfunylurea herbicide is azimusulfuron, flazasulfuron, thifensulfuron, flucetosufuron, mesosulfuron, or nicosulfuron . In some embodiments, the sulfonylurea herbicide is mesosulfuron .

Non-aqueous liquid carriers refer but is not limited to esters, amides, aromatic hydrocarbons, paraffins, petroleum, vegetable oil, alkyl ester of vegetable oils, alkyl phosphate, diesel, mineral oil, fatty acid amides, fatty acids, tall oil fatty acids, alkyl esters of fatty acids, modified vegetable oils and any combination thereof.

In some embodiments, the non-aqueous liquid carrier is selected_, from a group consisting of esters, amides, aromatic hydrocarbons, paraffins, petroleum, vegetable oil, alkyl ester of vegetable oils, alkyl phosphate, diesel, mineral oil, fatty acid amides, fatty acids, tall oil fatty acids, alkyl esters of fatty acids, modified vegetable oils and any combination thereof .

In some embodiments, the non-aqueous liquid carrier is selected from a group consisting of aromatic hydrocarbons, paraffins, petroleum, diesel, mineral oil, fatty acids, tall oil fatty acids, and any combination thereof.

In some embodiments, the non-aqueous liquid carrier is an aromatic hydrocarbon. In some embodiments, the non-aqueous liquid carrier is a combination of aromatic hydrocarbon and one or more additional non-aqueous liquid carrier.

In some embodiments, the aromatic hydrocarbon is selected from a group consisting of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene , isopropylbenzene , tert- butylbenzene , naphthalenes, and mono- or polyalkyl-substituted naphthalenes .

In some embodiments, the aromatic hydrocarbon is a CIO aromatic hydrocarbon. In some embodiments, the aromatic hydrocarbon is a C12 aromatic hydrocarbon. In some embodiments, the aromatic hydrocarbon is ultra-low naphthalene solvent (ULN) . In some embodiments, the aromatic hydrocarbon is low naphthalene solvent (LN) .

In some embodiments, the aromatic hydrocarbon is the Solvesso™ grades from ExxonMobil Chemical, especially Solvesso™ 100 (CAS No. 64742-95-6), Solvesso™ 150 (CAS No. 64742-94-5), and Solvesso™ 200 (CAS No. 64742-94-5) . In some embodiments, the aromatic hydrocarbon is Caromax™ 28 LN (sold by Petrochem Carless ) .

In some embodiments, the non-aqueous liquid carrier is a paraffin. In some embodiments, the paraffin is selected from a group consisting of octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, hepta-decane , octa-decane, nona-decane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and branched chain isomers thereof .

In some embodiments, the alkyl ester of fatty acid is a methyl ester of fatty acid. In some embodiments, the methyl ester of fatty acid is methyl caprylate/caprate. In some embodiments, the methyl caprylate/caprate is Stepan™ C-25 (sold by the Stepan Company) . In some embodiments, the non-aqueous liquid carrier is a vegetable oil. In some embodiments, the vegetable oil is selected from a group consisting of olive oil, kapok oil, castor oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cotton seed oil, soybean oil, rapeseed oil,_., linseed oil, tung oil, sunflower oil, safflower oil, and tall oil. In some embodiments, the non-aqueous liquid carrier is an alkyl ester of vegetable oil. In some embodiments, the alkyl ester of vegetable oils is selected from a group consisting of rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil propyl esters, rapeseed oil butyl esters, and tall oil fatty acids esters .

In some embodiments, the non-aqueous liquid carrier is a fatty acid amide. In some embodiments, the fatty acid amide is selected from a group consisting of C1-C3 amines, alkylamines and alkanolamines with C₆ - Cis carboxylic acids.

In some embodiments, the non-aqueous liquid carrier is an alkyl ester of fatty acids. In some embodiments, the alkyl ester of fatty acids is selected from a group consisting of C1-C4 monohydric alcohol esters of Cs to C22 fatty acids such as methyl oleate and ethyl oleate.

In some embodiments, the non-aqueous liquid carrier is substantially free of water. In some embodiments, the non^¬ aqueous liquid carrier comprises an amount of water less than or equal to 1.5%, or 1%, or 0.7%, or 0.5%, or 0.2% or 0.1% by weight. In some embodiments, the non-aqueous liquid carrier comprises 0.16% of water by weight. In some embodiments, the non-aqueous liquid carrier is free of water.

In some embodiments, the non-aqueous liquid formulation is substantially free of water. In some embodiments, the nonaqueous liquid formulation comprises water less than or equal to 1.5%, or 1%, or 0.7%, or 0.5%, or 0.2% or 0.1% by weight. In some embodiments, the non-aqueous liquid formulation comprises 0.16% of water by weight. In some embodiments, the non-aqueous liquid formulation is free of water.

In some embodiments, the amount of water in the non-aqueous liquid carrier is measured by Karl Fischer titration. In some embodiments, the amount of water in the non-aqueous liquid formulation is measured by Karl Fischer titration. In some embodiments, the non-aqueous liquid carrier has no basic nature .

In some embodiments, the non-aqueous liquid carrier is other than vegetable oil. In some embodiments, the non-aqueous carrier is other than rapeseed oil. In some embodiments, the non-aqueous carrier is other than rapeseed oil methyl ester.

In some embodiments, the non-aqueous liquid carrier is other than dimethyl amides of fatty acids. In some embodiments, the non-aqueous carrier is other than methyl ester of fatty acids. In some embodiments, the non-aqueous carrier is other than morpholine amides of fatty acids.

In some embodiments, the non-aqueous liquid carrier is other than N-octyl-2-pyrrolidone .

In some embodiments, the amount of the flufenacet is 0.1-80% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the flufenacet is 0.1-70% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the flufenacet is 1-60% by weight based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 5-50% by weight based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 1-15% by weight based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 10-20% by weight based on the total weight of the stable formulation. In some embodiments, the amount of flufenacet is 13% by weight based on the total weight of the stable formulation.

In some embodiments, the concentration of the flufenacet in the stable formulation is between 50 to 500 g/L. In some embodiments, the concentration of the flufenacet in the stable formulation is between 50 to 300 g/L. In some embodiments, the concentration of the flufenacet in the stable formulation is between 100 to 200 g/L. In some embodiments, the concentration of the flufenacet in the stable formulation is between 100 to 150 g/L. In some embodiments, the concentration of the flufenacet in the stable formulation is about 128 g/L.

In some embodiments, the amount of the sulfonylurea herbicide is 0.1-80% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the sulfonylurea herbicide is 0.1-70% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the sulfonylurea herbicide is 0.1-60% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the sulfonylurea herbicide is 0.1-40% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the sulfonylurea herbicide is 0.1-25% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the sulfonylurea herbicide is 0.1-1% by weight based on the total weight of the stable formulation. In a specific embodiment, the amount of the sulfonylurea herbicide is 0.5% by weight based on the total weight of the stable formulation.

In some embodiments, the concentration of the sulfonylurea in the stable formulation is between 1 to 50 g/L. In some embodiments, the concentration of the sulfonylurea in the stable formulation is between 1 to 25 g/L. In some embodiments, the concentration of the sulfonylurea in the stable formulation is between 1 to 10 g/L. In some embodiments, the concentration of the sulfonylurea in the stable formulation is about 5 g/L.

In some embodiments, the amount of the flufenacet and the at least one sulfonylurea herbicide is 0.1-90% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the flufenacet and the at least one sulfonylurea herbicide is 0.5-30% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the flufenacet and the at least one sulfonylurea herbicide is 1-15% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the flufenacet and the at least one sulfonylurea herbicide is 1-10% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the flufenacet and the at least one sulfonylurea herbicide is 3-8% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the flufenacet and the at least one sulfonylurea herbicide is about 15% by weight based on the total weight of the stable formulation .

In some embodiments, the concentration of the flufenacet and the sulfonylurea in the stable formulation is between 50 to 500 g/L. In some embodiments, the concentration of the flufenacet and the sulfonylurea in the stable formulation is between 50 to 300 g/L. In some embodiments, the concentration of the flufenacet and the sulfonylurea in the stable formulation is between 100 to 200 g/L. In some embodiments, the concentration of the flufenacet and the sulfonylurea in the stable formulation is between 100 to 150 g/L. In some embodiments, the concentration of the flufenacet and the sulfonylurea in the stable formulation is about 132 g/L.

In some embodiments, the amount of the non-aqueous liquid carrier is 10-90% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the non-aqueous liquid carrier is 40-90% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the non-aqueous liquid carrier is 50-80% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the non-aqueous liquid carrier is 60-80% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the non-aqueous liquid carrier is 70-80% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the non-aqueous liquid carrier is 75- 80% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the non-aqueous liquid carrier is 77% by weight based on the total weight of the stable formulation.

In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 300-900 g/L. In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 400-700 g/L. In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 500-600 g/L. In some embodiments, the concentration of the non-aqueous liquid carrier in the stable formulation is 575-600 g/L.

In some embodiments, the formulation comprises at least one surfactant .

Surfactants may include but are not limited to alkyl-end-capped ethoxylate glycol, alkyl-end-capped alkyl block alkoxylate glycol, dialkyl sulfosuccinate , phosphated esters, alkyl sulfonates, alkyl aryl sulfonates, tristyrylphenol alkoxylates, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether) , block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers) or combinations thereof.

In a preferred embodiments, surfactant is an alkyl-end-capped alkoxylate. In some embodiments, the adjuvant is a methyl-end- capped ethoxylate. In some embodiments, the adjuvant is a methyl- end-capped tridecyl ethoxylate. In some embodiments, the adjuvant is a methyl-end-capped tridecyl ethoxylate with six ethylene oxides.

In some embodiment the surfactant is Genapol® XM-60. Genapol® XM-60 (CAS No. 345642-79-7, sold by Clariant) is a methyl-end- capped ethoxylate based on Genapol® X 060 (CAS No. 9043-30-5, sold by Clariant) .

In a preferred embodiment, the surfactant is selected from group consisting of synthetic end capped alcohol alkoxylates and alkyl aryl sulphonates . In some embodiments, the surfactant is calcium dodecylbenzene sulfonate. In some embodiments, the surfactant is Nansa® EVM 70/2E (sold by Huntsman International LLC) . In some embodiments, the surfactant is other than an isotridecyl alcohol polyglycol ether (6EO) . In some embodiments, the surfactant is other than an isotridecyl alcohol polyglycol ether (8EO) . In some embodiments, the surfactant is other than Genapol® X 060. In some embodiments, the surfactant is other than Genapol® X 080 (CAS 9043-30-5, sold by Clariant) . In some embodiments, the surfactant is other than an anionic sulfosuccinate . In some embodiments, the surfactant is other than a dioctyl sulfosuccinate . In some embodiments, the surfactant is other than 1 , 4-Bis ( 2-ethylhexyl ) sodium sulfosuccinate . In some embodiments, the surfactant is other than TRITON™ GR-7ME (CAS No. 577-11-7, sold by The Dow Chemical Company) or TRITON™ GR- 7M (CAS No. 577-11-7, sold by The Dow Chemical Company) . In some embodiments, the surfactant is other than a mixture of fatty acid polyethylene glycol esters. In some embodiments, the surfactant is other than ALKAMULS® VO/2003 (CAS No. 220037-02- 5, sold by Rhodia Operations, a member of the SOLVAY Group.

In some embodiments, the amount of surfactants present in the stable formulation is between 0.1-40% by weight based on the total weight of the stable formulation. In some embodiments, the amount of surfactants present in the stable formulation is between 0.1-35% by weight based on the total weight of the stable formulation. In some embodiments, the amount of surfactants present in the stable formulation is between 0.1-30% by weight based on the total weight of the stable formulation. In some embodiments, the amount of surfactants present in the stable formulation is between 1-20% by weight based on the total weight of the stable formulation. In some embodiments, the amount of surfactants present in the stable formulation is between 5-10% by weight based on the total weight of the stable formulation. In some embodiments, the amount of surfactants present in the stable formulation is about 17% by weight based on the total weight of the formulation.

In some embodiments, the formulation further includes at least one adjuvant . In some embodiments, the adjuvant is selected from a group consisting of alkyl ethoxylate glycol, alkyl block alkoxylate glycol, alkyl-end-capped ethoxylate glycol, alkyl-end-capped alkyl block alkoxylate glycol, dialkyl sulfosuccinate, ethoxylated alcohols, phosphated esters, ethoxylated tristyryl phenol phosphate, sorbitan esters, Tween esters and combinations thereof .

In this regard, when a nonionic surface active agent of alkyl- end-capped ethoxylate glycol, alkyl-end-capped alkyl block alkoxylate glycol is used as the emulsifier, it can also function as an adjuvant.

In some embodiments, the adjuvant is added to the formulation as tank mix, simultaneously or separately.

In some embodiments, the adjuvant is present in an amount of at least 0.1% by weight based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 5% by weight based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 10% by weight based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 15% by weight based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 20% by weight based on the total weight of the stable formulation. In some embodiments, the adjuvant is present in an amount of at least 30% by weight based on the total weight of the stable formulation.

In some embodiments, the formulation further include additional physical stabilizer such as buffers, acidifiers, defoaming agents, thickeners and drift retardants.

Thickener useful herein are silica, silica organo modified bentonites, inorganic clays and any combination thereof.

Silica may be a fumed and precipitated silica and any combination thereof . Fumed and precipitated silica may be hydrophobic and hydrophilic silica and any combination thereof.

Examples of fumed silica that may include in the formulation of the subject invention but are not limited to Aerosil® A 200, Aerosil® R 202, Aerosil® R 972 and Aerosil® R 805 (all sold by Evonik) .

Examples of precipitated silica that may include in the formulation of the subject invention but are not limited to Sipernat® 22S (sold by Evonik) , Sipernat® D17 (sold by Evonik) and Tixosil® 38 (sold by Rhodia Operations, a member of the Solvay Group) .

An example of organo modified bentonite that may be used in the formulation of the subject invention is Bentone® SD-1 (sold by Elementis Specialties) .An example of inorganic clays that may be used in the formulation of the subject invention is Attagel® 40 (sold by BASF) .

Other examples of adjuvants that may be used in the formulations of the subject invention include sticking agents, spreading agents, synergists, penetrants, compatibility agents, buffers, acidifiers, defoaming agents, and drift retardants .

In some embodiments, the stable formulation further comprises a safener .

In some embodiments, the safeners is selected from a group consisting of mefenpyr diethyl, cloquintocet mexyl, fenchlorazole ethyl, benoxacor, dichlormid, isoxadifen ethyl, and any combination thereof. In preferred embodiments, the safener is mefenpyr diethyl.

In some embodiments, the safener is added to the formulation as tank mix, simultaneously or separately. In some - embodiments, the amount of the safener in the stable formulation is 0.1-80% by weight based on the total weight of the stable formulation. In some embodiments, the amount of safener in the stable formulation is 1-50% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the safener in the stable formulation is 1-25% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the safener in the stable formulation is 1-15% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the safener in the stable formulation is 1-10% by weight based on the total weight of the stable formulation. In some embodiments, the amount of the safener in the stable formulation is 1-5% by weight based on the total weight of the stable formulation.

Other ingredients, such as adhesives, neutrali zers , binders, sequestrates, biocides, stabilizers, buffers preservatives, antioxidants or anti-freeze agents, may also be added to the present compositions in order to increase the stability, density, and viscosity of the described compositions.

In some embodiments, the stable formulation is an oil formulation. In some embodiments, the stable formulation is an oil dispersible formulation.

In one embodiment, the stable formulation comprises: a) 1.0-15% by weight of flufenacet; b) 0.1-25% by weight of at least one sulfonylurea herbicide; c) 10-90% by weight of a non-aqueous liquid carrier; and d) optionally, 0.1-30% by weight of safener and/or adjuvant.

In some embodiments, the formulation is stable after 7 days in storage. In some embodiments, the formulation is stable after 10 days in storage. In some embodiments, the formulation is stable after 14 days.

In some embodiments, the formulation is stored at a temperature between 20 to 55 °C. In some embodiments, the formulation is stored at a temperature between 40 to 55 °C. In some embodiments, the formulation is stored at a temperature between 50 to 55°C. In some embodiments, the formulation is stored at a temperature of 54°C.

In some embodiments, the formulation is stable after 14 days in storage at a temperature of 54°C.

In some embodiments, the formulation comprises less than 5% of flufenacet N-isomer. In some embodiments, the formulation comprises less than 2% of flufenacet N-isomer. In some embodiments, the formulation comprises less than 1% of flufenacet N-isomer. In some embodiments, the formulation comprises less than 0.5% of flufenacet N-isomer. In some embodiments, the formulation comprises less than 0.1% of flufenacet N-isomer. In some embodiments, the formulation comprises an undetectable amount of flufenacet N-isomer. In some embodiments, the formulation comprises no flufenacet N-isomer.

Further, the agricultural compositions herein may be used in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the herein described composition may be formulated with the other pesticide ( s ) , tank mixed with the other pesticide (s) or applied sequentially with the other pesticide (s) . In addition, the herein described composition may, optionally, be combined with or blended with other pesticide composition ( s ) . This blend with pesticide composition ( s ) may be used to control pests in crops and non-crop environments.

Methods of use of the formulations described herein

The formulations described herein are suitable for the control of weed. ~"

The subject invention also provides a method for controlling weed comprising applying the stable herbicidal non-aqueous liquid formulation described herein to a weed, a portion of a weed, an area or soil adjacent to a weed, and/or a seed of a weed so as to thereby control the weed. The subject invention also provides a method of controlling weed comprising : a) obtaining a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet, an amount of at least one sulfonylurea herbicide, and an agrochemically acceptable non-aqueous liquid carrier, wherein in the flufenacet is dissolved in the non-aqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier, and b) applying the stable herbicidal non-aqueous liquid formulation to a weed, a portion of a weed, an area or soil adjacent to a weed, and/or a seed of a weed so as to thereby control the weed. Methods include adding the stable herbicidal non-aqueous liquid formulation to a carrier such as water and using the resulting solution containing the herbicidal organic formulation for spray applications to control weeds in plant or plant propagation material thereof in crop or non-crop environments. By diluting the stable herbicidal non-aqueous liquid formulation in water (i.e. affirmatively adding water to the formulation), a suspo- emulsion may be formed.

Effective application rates of the herbicidal composition cannot generally be defined, as it varies depending upon various conditions such as the type of weed, weather conditions, nature of the soil, and the type of crop.

In one embodiment, the stable herbicidal non-aqueous liquid formulation is generally applied at a rate of about 1 to about 5 L/ha. In a preferred embodiment the stable herbicidal non- aqueous liquid formulation is applied at a rate of about 2 to 3 L/ha. In a specific embodiment the stable herbicidal non-aqueous liquid formulation is applied at a rate of about 2 L/ha. In another specific embodiment the stable herbicidal non-aqueous liquid formulation is applied at a rate of about 3 L/ha. In another specific embodiment the stable herbicidal non-aqueous liquid formulation is applied at a rate of about 2.5 L/ha.

In an embodiment, the stable herbicidal non-aqueous liquid formulation may be diluted in a carrier such as water in an amount of from about 1 to 100 L of the stable formulation per 1000L of water. In a further embodiment, the stable herbicidal non-aqueous liquid formulation may be diluted in a carrier such as water in an amount of from about 1 to 30 L of the stable formulation per 1000 L of water. In yet another embodiment, the stable herbicidal non-aqueous liquid formulation may be diluted in a carrier such as water in an amount of from about 5 to 15 L of the stable formulation per 1000L of water.

In some embodiments, crop plants may include, but are not limited to, cereals, soybean, corn, rice, papaya, melon, cacao and coffee.

Cereals may include, but are not limited to, wheat, barley, rye and oats.

In another embodiment, the weeds may include, but are not limited to, grass weeds such as Poa, Lolium and broad leaves. The stable herbicidal non-aqueous liquid formulation described herein may be mixed with water and/or fertilizers and may be applied to a desired locus by any means, such as airplane spray tanks, knapsack spray tanks, cattle dipping vats, farm equipment used in ground spraying (e.g., boom sprayers, hand sprayers), and the like. The desired locus may be soil, plants, and the like.

The present stable herbicidal non-aqueous liquid formulation may include additional crop protection agents, for example insecticides, herbicides, fungicides, bactericides, nematicides, molluscicides , growth regulators, biological agents, fertilizers, or mixtures thereof. When used in conjunction with additional crop protection agents, the composition can be formulated with these co-agents, tank mixed with these co-agents or applied sequentially with these co- agents .

Processes of preparation for the formulations described herein

The present invention provides a process for preparing a stable herbicidal non-aqueous liquid formulation comprising an effective amount of flufenacet and an effective amount of at least one sulfonylurea herbicide, wherein the process comprises the steps of:

(i) dissolving the flufenacet in a non-aqueous carrier to form a solution;

(ii) adding the sulfonylurea herbicide to the solution of step (i) to form a suspension; and

(iii) milling the suspension to obtain the stable formulation.

In some embodiments, the non-aqueous carrier -is added during step (ii) .

In some embodiments, the process further comprise a step of adding at least one surfactant and/or adjuvant to the solution of step (i)- prior to performing step (ii) . In some embodiments, the process further comprise a step of adding at least one surfactant and/or adjuvant to the solution of step (ii) prior to performing step (iii) .

In some embodiments, the process further comprise a step of adding a safener to the solution of step (i) prior to performing step (ii) . In some embodiments, the safener is mefenpyr diethyl.

In some embodiments, the process further comprise a step of adding at least one surfactant to the solution of step (i) prior to performing step (ii) . In some embodiments, the surfactant is calcium dodecylbenzene sulfonate and/or methyl-end-capped ethoxylate .

In some embodiments, the process further comprises a step of adding a thickener to the suspension of step (ii) prior to performing step (m) . In some embodiments, the thickener is fumed silica.

In some embodiments, the non-aqueous liquid carrier is heated to completely dissolve the flufenacet and/or the additives. Additives may include, but are not limited to, safener and adjuvant .

In some embodiments, step (i) is performed at a temperature between 15°C to 65°C. In some embodiments, step (i) is performed at a temperature of about 20°C, 30°C, 40°C, 50°C or 60°C.

In some embodiments, the suspension is milled until 90% of the particles have a particle size of about 1-10μ. In some embodiments, the suspension is milled until 90% of the particles have a particle size of less than 8μ.

For the foregoing embodiments, each embodiment disclosed herein is contemplated as being applicable to each of the other disclosed embodiments. In addition, the elements recited in formulation embodiments can be used in the method and use embodiments described herein and vise versa.

This invention will be better understood by reference to the Experimental Section which follows, but those skilled in the art will readily appreciate that the specific experiments detailed are only illustrative of the invention as described more fully in the claims which follow thereafter.

Experimental Section

Combining sulfonylurea herbicides and flufenacet into one formulation is particularly challenging because sulfonylurea herbicides and flufenacet a generally stable under different conditions. In addition, flufenacet is highly sensitive and rapidly decomposes under various conditions.

In particular, sulfonylurea herbicides are stable in pH value more than 7 and hydrolyze rapidly in aqua and/or acid environment. Flufenacet, on the other hand, is stable in acidic conditions. In neutral or basic conditions, flufenacet decomposes, wherein one of the decomposed product is N-isomers which are less active and/or more toxic.

Attempts to combine a sulfonylurea herbicide, e.g., mesosulfuron, and flufenacet into one formulation have failed numerous times.

In water-based suspension concentrate or suspo-emulsion formulations, mesosulfuron decomposes due to presence of water. In water dispersible granules formulations, depending on the pH of the formulation (after dilution in water) , one of the actives always showed decomposition. Specifically, flufenacet decomposed during accelerated storage where pH > 7 (pH = 8) while mesosulfuron decomposed during accelerated storage where pH < 7 (pH = 4) .

In an oil dispersion formulation in vegetable oil where both actives are in dispersion, the flufenacet particles crystalized. In oil dispersion formulations wherein mesosulfuron is dispersed in the solvent while flufenacet is dissolved in the solvent, the stability of the formulation depended on the solvent and surfactant used. In fact, approximately 20 different experiments with different surfactants and solvents were tried to arrive at the stable formulation described in the examples below. Example 1 :

Mesosulfuron, Flufenacet and Mefenpyr Diethyl Oil Dispersion (OP) Formulation

5/125/15

Flufenacet Tech (128 g) (provided by Jiangsu Luye (China) ) and Mefenpyr Diethyl (16 g) were dissolved in 795.3 g of Caromax™ 28 LN. The mixture was heated to 50° C to enhance dissolution. When everything was dissolved Nansa® EVM 70/2E (6.2 g) and Genapol® XM-60 (56.1 g) were added and mixed to uniformity. When uniform, 5.3 g of Mesosulfuron Tech and 31.1 g of fumed silica were added and uniformly dispersed in the solution. The dispersion was milled in a bead mill to a particle size D (90%) less than 8 μ. The oil dispersion formulation of flufenacet 125 mesosulfuron 5 mefenpyr diethyl 15 was subjected to accelerated storage stability test - 14 days @ 54°C. All active ingredients were found to be stable. No decomposition product of flufenacet (such as N-isomer) were found after accelerated storage. The stable herbicidal non-aqueous liquid formulation exemplified above has significant advantages over the mixtures and formulations which are known in the art. The formulation is physically stable and easy to use in the fields.

To evaluate the effectiveness of the formulations of the subject invention when used with crops, the formulation was applied to wheat and the results showed that the herbicidal non-aqueous liquid formulation performed at least as well as mixtures and formulations known in the art.

While the present invention has been shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that many alternatives, modifications and variations may be made thereto without departing from the spirit and scope thereof. Accordingly, it is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and broad scope of the appended claims.

All publications, patents and patent applications mentioned in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated herein by reference.

Claims

CLAIMS :

1. A stable herbicidal non-aqueous liquid formulation comprising : a) an amount of flufenacet;

b) an amount of at least one sulfonylurea herbicide; and c) an agrochemically acceptable non-aqueous liquid carrier, wherein in the flufenacet is dissolved in the non-aqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier.

2. The stable formulation of claim 1, wherein the sulfunylurea herbicide is selected from the group consisting of azimusulfuron, flazasulfuron, thifensulfuron, flucetosufuron, mesosulfuronand nicosulfuron .

3. The stable formulation of claim 1 or 2, wherein the sulfonylurea herbicide is mesosulfuron .

4. The stable formulation of any one of claims 1-3, wherein the non-aqueous liquid carrier is selected from a group consisting of aromatic hydrocarbons, paraffins, petroleum, diesel, mineral oil, fatty acid amides, fatty acids, tall oil fatty acids, alkyl esters of fatty acids, modified vegetable oils and any combination thereof.

5. The stable formulation of claim 4, wherein the non-aqueous carrier is selected from a group consisting of aromatic hydrocarbons, paraffins, petroleum, diesel, mineral oil, fatty acids, tall oil fatty acids, and any combination thereof .

6. The stable formulation of any one of claims 1-5, wherein the non-aqueous liquid carrier is an aromatic hydrocarbon.

7. The stable formulation of claim 6, wherein the aromatic hydrocarbon is selected from a group consisting of toluene, o-xylene , m-xylene , p-xylene , ethylbenzene, isopropylbenzene, tert-butylbenzene , naphthalenes, mono- or polyalkyl-substituted naphthalenes, CIO aromatic hydrocarbon and C12 aromatic hydrocarbon.

8. The stable formulation of any one of claims 1-7, wherein non-aqueous liquid carrier is a low naphthalene solvent.

9. The stable formulation of any one of claims 1-8, wherein the non-aqueous liquid carrier is an ultra-low naphthalene solvent .

10. The stable formulation of any one of claims 1-9, wherein the amount of flufenacet is 0.1-80% by weight based on the total weight of the stable formulation.

11. The stable formulation of any one of claims 1-10, wherein the amount of flufenacet is 10-20% by weight based on the total weight of the stable formulation.

12. The stable formulation of any one of claims 1-11, wherein amount of the sulfonylurea herbicide is 0.1-80% by weight based on the total weight of the stable formulation.

13. The stable formulation of any one of claims 1-12, wherein the amount of the sulfonylurea herbicide is 0.1-25% by weight based on the total weight of the stable formulation.

14. The stable formulation of any one of claims 1-13, wherein the amount of the sulfonylurea herbicide is 0.1-1% by weight based on the total weight of the stable formulation.

15. The stable formulation of any one of claims 1-14, wherein the amount of the non-aqueous liquid carrier is 10-90% by weight based on the total weight of the stable formulation.

16. The stable formulation of any one of claims 1-15, wherein the amount of the non-aqueous liquid carrier is 70-80% by weight based on the total weight of the stable formulation.

The stable formulation of any one of claims 1-16 further comprising at least one adjuvant.

The stable formulation of claim 17, wherein the adjuvant is added to the formulation as tank mix.

The stable formulation of claim 17 or 18, wherein the adjuvant is present in an amount of at least 0.1% by weight based on the total weight of the stable formulation.

The stable formulation of any one of claims 17-19, wherein the adjuvant is a surfactant selected from a group consisting of alkyl-end-capped ethoxylate glycol, alkyl- end-capped alkyl block alkoxylate glycol, dialkyl sulfosuccinate, phosphated esters, alkyl sulfonates, alkyl aryl sulfonates, tristyrylphenol alkoxylates, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols, block copolymers, and any combination thereof.

The stable formulation of claim 20, wherein the surfactant is an alkyl-end-capped alkoxylate or adjuvant is di alkyl end capped poly alkoxy glycol.

The stable formulation of claim 21, wherein the alkyl-end- capped alkoxylate is a methyl-end-capped tridecyl ethoxylate with six ethylene oxides.

The stable formulation of claim 20, wherein the surfactant is selected from group consisting of synthetic alcohol alkoxylates and alkyl aryl sulphonates.

The stable formulation of claim 23, wherein the surfactant is calcium dodecyl benzene sulphonate .

The stable formulation of any one of claims 20-24, wherein the amount of surfactant present in the stable formulation is between 0.1-40% by weight based on the total weight of the stable formulation.

The stable formulation of any one of claims 20-25, wherein the amount of surfactant present in the stable formulation is 5-10% by weight based on the total weight of the formulation ..

The stable formulation of any one of claim 17-26, wherein at least one of the adjuvants is a thickener.

The stable formulation of claim 27, wherein the thickener is selected from a group consisting of fumed silica, precipitated silica, organo modified bentonites, inorganic clays, and any combination thereof.

The stable formulation of claim 28, wherein the thickener is fumed silica.

The stable formulation of any one of claims 1-29 further comprising a safener.

The stable formulation of claim 30, wherein the safener is selected from a group consisting of mefenpyr diethyl, cloquintocet mexyl, fenchlorazole ethyl, benoxacor, dichlormid, isoxadifen ethyl, and any combination thereof.

The stable formulation of claim 31, wherein the safener is mefenpyr diethyl.

The stable formulation of any one of claims 30-32, wherein the safener is added to the formulation as tank mix.

The stable formulation of any one of claims 30-33, wherein amount of the safener in the stable formulation is 0.1-80% by weight based on the total weight of the stable formulation.

The stable formulation of any one of claims 30-34, wherein the amount of the safener in the stable formulation is 1- 5% by weight based on the total weight of the stable formulation .

The stable formulation of any one of claims 1-35, wherein the formulation comprises: a) 0.1-25% by weight of at least one sulfonylurea herbicide ; b) 1.0-15% by weight of flufenacet; c) 10-90% by weight of a non-aqueous liquid carrier; and d) optionally, 0.1-30% by weight of safener and/or adj uvant .

The stable formulation of any one of claims 1-36, wherein the stable formulation is an oil dispersible formulation.

The stable formulation of any one of claims 1-37, wherein the formulation is stable after 14 days in storage at temperature of 54 °C.

The stable formulation of any one of claims 1-38, wherein the formulation comprises less than 5% of flufenacet N- isomer.

The stable formulation of any one of claims 1-39, wherein the non-aqueous liquid carrier comprises equal to or less than 1.5% of water by weight.

41. The stable formulation of any one of claims 1-40, wherein the stable formulation comprises equal to or less than 1.5% of water by weight.

42. An herbicidal suspo-emulsion formulation comprising the stable formulation of any one of claims 1-41.

43. A method for controlling weed comprising applying the formulation of any one of claims 1-42 to a weed, a portion of a weed, an area or soil adjacent to a weed, and/or a seed of a weed so as to thereby control the weed.

44. A method of controlling weed comprising: a) obtaining a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet, an amount of at least one sulfonylurea herbicide; and an agrochemically acceptable non-aqueous liquid carrier, wherein in the flufenacet is dissolved in the nonaqueous liquid carrier and the sulfonylurea herbicide is suspended in the non-aqueous liquid carrier, and b) applying the stable herbicidal formulation to a weed, a portion of a weed, an area or soil adjacent to _a weed, and/or a seed of a weed so as to thereby control the weed.

45. The method of claim 43 or 44, wherein the formulation is applied at a rate of about 1 to about 5 L/ha.

46. The method of any one of claims 43-45, wherein the formulation is diluted in a carrier in an amount of from about 1 to 100 L of the stable formulation per 1000L of the carrier.

47. The method of any one of claims 43-46 for controlling weed in plant or plant propagation material thereof.

48. The method of claim 47, wherein the plant is cereal, soybean, corn, rice, papaya, melon, cacao or coffee.

49. The method of any one of claims 43-48, wherein the weed is Poa, Lolium or broad leaves.

50. A process for preparing a stable herbicidal non-aqueous liquid formulation comprising an amount of flufenacet and an amount of at least one sulfonylurea herbicide, wherein the process comprises the steps of:

(i) dissolving the flufenacet in a non-aqueous carrier to form a solution; (ϋ) adding the sulfonylurea herbicide to the solution of step (i) to form a suspension; and milling the suspension to obtain the stable formulation .

51. The process of claim 50, wherein the process further comprises a step of adding at least one adjuvant to the solution of step (i) prior to performing step (ii) .

52. The process of claim 50 or 51, wherein the process further comprise a step of adding at least one adjuvant to the solution of step (ii) prior to performing step (iii) .

53. The process of claim 51 or 52, wherein the adjuvant is a surfactant .

54. The process of claim 53, wherein the surfactant is calcium dodecylbenzene sulfonate and/or methyl-end-capped ethoxylate .

55. The process of any one of claims 50-54, wherein the process further comprises a step of adding a thickener to the suspension of step (ii) prior to performing step (iii) .

56. The process of claim 53, wherein the thickener is fumed silica .

57. The process of any one of claims 50-56, wherein the process further comprise a step of adding a safener to the solution of step (i) prior to performing step (ii) .

58. The process of claim 57, wherein the safener is mefenpyr diethyl .

59. The process of any one of claims 50-58, wherein the nonaqueous liquid carrier is heated to completely dissolve -the flufenacet and/or the additives.

60. The process of any one of claims 50-59, wherein step (i) is performed at a temperature between 15°C to 65°C.