GB2626177A

GB2626177A - Herbicidal composition comprising pinoxaden

Info

Publication number: GB2626177A
Application number: GB2300519.2A
Authority: GB
Inventors: Lee Ng Na
Original assignee: Rotam Agrochem International Co Ltd
Current assignee: Rotam Agrochem International Co Ltd
Priority date: 2023-01-13
Filing date: 2023-01-13
Publication date: 2024-07-17
Also published as: GB202300519D0

Abstract

A herbicidal emulsion concentrate comprising pinoxaden, cloquintocet-mexyl, a phosphite ester of formula (I), wherein R is independently C1-C12 alkyl or phenyl, a solvent and an emulsifier. A use and method for controlling unwanted plant growth comprising applying the composition to plants is also included. Uses and methods of the phosphite ester to independently increase the stability of pinoxaden or cloquintocet-mexyl in an emulsion concentrate are also included. Pinoxaden may be present at 1-200 g/L, preferably 10-100 g/L, cloquintocet-mexyl may be present at 0.5-50 g/L, preferably 1-25 g/L, and the phosphite ester may be present at 50-600 g/L, preferably 10-500 g/L. The weight ratio of pinoxaden to phosphite ester may be between 2:1 and 25:1 and the weight ratio of cloquintocet-mexyl to phosphite ester may be between 10:1 and 45:1. The solvent may be aromatic hydrocarbons, alcohols, ketones, amides and esters. The emulsifier may be alkyl sulphonates, vegetable oil alkoxylates, alkylphenol epoxides or ethylene oxide and propylene oxide block copolymers. The composition may comprise 10-110 g/L pinoxaden, 1-25 g/L cloquintocet-mexyl, 100-500 g/L phosphite ester, 100-800 g/L solvent and 1-200 g/L emulsifier.

Description

HERBICIDAL COMPOSITION COMPRISING PINOXADEN

The present invention relates to a herbicidal composition comprising pinoxaden, in particular to a composition in the form of an emulsifiable concentrate.

The present invention further relates to the preparing of the emulsifiable concentrate and its use in the control of plant growth.

[8-(2,6-diethyl-4-methylpheny1)-1,2,4,5-tetrahydro-7-oxo-7H-pyrazolo[1, 2-d][1,4,5]oxadiazepin-9-y1-2,2-dimethylpropionate has the Chinese name zuolincaozhi and the English common name of pinoxaden The compound has the following structural formula: kk, F-1;:3C-''''

CH

Pinoxaden is a known herbicide and is commercially available. Pinoxaden and a preparation method therefor are known from WO 99/47525. Pinoxaden is a selective systemic herbicide and is used, for example, to control monocotyledonous grass weeds in crops such as wild oats, rye-grass and black grass in winter and spring wheat and winter and spring barley.

Commercial formulations of pinoxaden in the form of emulsifiable concentrates (EC) are available from Syngenta in many countries; for example, in the United States, they are available under the trademarks AxialTM and Axial XLTM. -2 -

1-methylhexyl(5-chloro-8-quinolinoxy)acetate, or (1-methylhexyl) (5-chloroquinoline-8-yloxy)acetate has the Chinese name jiecaozhi and the English common name of Cloquintocet-mexyl. Cloquintocet-mexyl has the following structural formula: A preparation method for cloquintocet-mexyl is known from US 4902340. Cloquintocet-mexyl is a known safener for herbicides and is commercially available.

Example Fl of WO 99/047525 describes an emulsifiable concentrate of pinoxaden. However, such emulsifiable concentrates exhibit a poor stability. After a period of time, the pinoxaden is decomposed or modified, for example by hydrolysis or transesterification with a corresponding loss of herbicidal activity.

WO 2007/073933 discloses an emulsifiable concentrate (EC) formulation comprising pinoxaden and attempts to address the stability problems arising with the formulations of WO 99/047525. It is disclosed that an alcohol may be added as a solvent to the formulation or a ketone solvent in the formulation may be replaced with an alcohol solvent to improve the storage stability. WO 2007/073933 disclosed working examples of EC formulations comprising pinoxaden in combination with cloquintocet-mexyl.

AU 2019100546 also addresses the issue of the stability of pinoxaden in EC formulations. This document discloses that a combination of at least two of solvents selected acetophenone, propylene carbonate and butylene carbonate, -j -and N-(C1-C4)alkylpyrrolidone may used to improve the stability of pinoxaden in a emulsifiable concentrate (EC) formulation. EC formulations of pinoxaden containing cloquintocet-mexyl as a safener are disclosed.

WO 2008/049618 discloses that tris-esters of phosphoric acid and/or bis- esters of alkyl phosphonic acids with aliphatic or aromatic alcohols, such as tri-(2-ethylhexyl)phosphate, may be used to improve the stability of pinoxaden in an emulsifiable concentrate (EC) formulation. Again, formulations containing cloquintocet-mexyl as a safener are disclosed.

More recently, WO 2014/060557 discloses a combination of pinoxaden and cloquintocet-mexyl, which comprises a polymerization thickening agent and an alcohol-containing solvent system.

A review of the prior art shows that attention has been paid to improving the stability, for example the storage or thermal stability, of pinoxaden in emulsifiable concentrate (EC) formulations. However, little to no attention has been paid to the degradation of cloquintocet-mexyl present in such formulations as a safener, in particular the stability of the safener during storage. Therefore, there is a need for an improved emulsifiable concentrate (EC) formulation comprising pinoxaden and cloquintocet-mexyl, preferably a formulation that exhibits improved stability of both pinoxaden and cloquintocet-mexyl. It would be very advantageous is the improved formulation could exhibit an improved stability of both components during storage.

It has unexpectedly been found that the addition of a phosphite ester to an emulsifiable concentrate (EC) formulation containing pinoxaden and cloquintocetmexyl can improve the storage stability of both pinoxaden and cloquintocet-mexyl.

In a first aspect, the present invention provides a herbicidal composition in the form of an emulsifiable concentrate (EC), the herbicidal composition comprising: (1) pinoxaden; (2) cloquintocet-mexyl, -4 - (3) a phosphite ester having a general formula (I).

Formula wherein each R is independently a Ci to Ci2 alkyl group or a phenyl group; (4) at least one solvent; and (5) at least one emulsifier.

In the herbicidal composition according to the present invention, the presence of the auxiliary agent of a phosphite ester of formula I unexpectedly leads to a significant stabilizing effect on the pinoxaden and cloquintocet-mexyl present in the emulsifiable concentrate. Unexpectedly, little to no hydrolysis or transesterification of pinoxaden is observed in the composition, while in addition little to no hydrolysis or transesterification of cloquintocet-mexyl is observed.

The emulsifiable concentrate (EC) comprises pinoxaden as an active herbicidal component. Pinoxaden may be present in any suitable amount to provide the required herbicidal activity. The composition may comprise pinoxaden in an amount of up to 400 g/L, preferably up to 350 g/L, more preferably up to 300 g/L, still more preferably up to 250 g/L, more preferably still up to 200 g/L, especially up to 150 g/L, more especially up to 100 g/L. The composition may comprise pinoxaden in an amount of from 1 g/L, preferably from 2 g/L, more preferably from 3 g/L, still more preferably from 5 g/L, more preferably still from 6 g/L, especially from 8 g/L, more especially from 10 g/L. Preferred embodiments of the composition comprise pinoxaden in an amount of from 1 to 300 g/L, more preferably from 5 to 200 g/L, and especially from 10 to 100 g/L. -5 -

The emulsifiable concentrate (EC) composition further comprises cloquintocet-mexyl. Cloquintocet-mexyl functions as a saferner. Cloquintocetmexyl may be present in the composition in an amount of up to 200 g/L, preferably up to 150 g/L, more preferably up to 125 g/L, still more preferably up to 100 g/L, more preferably still up to 75 g/L, especially up to 50 g/L, more especially up to 25 g/L. The composition may comprise cloquintocet-mexyl in an amount of from 0.1 g/L, preferably from 0.2 g/L, more preferably from 0.3 g/L, still more preferably from 0.5 g/L, more preferably still from 0.6 g/L, especially from 0.8 g/L, more especially from 1 g/L. Preferred embodiments of the composition comprise cloquintocet-mexyl in an amount of from 0.1 to 100 g/L, more preferably from 0.5 to 50 g/L, and especially from 1 to 25 g/L.

The emulsifiable concentrate (EC) composition further comprises a phosphite ester having a general formula (I): 0., Fomtla In the phoshpites of general formula I, each R is independently selected to be a Ci to C12 alkyl group or a phenyl group Two or more groups represented by R in the general formula I may be the same. In many preferred embodiments, all three groups represented by R are the same.

Each R may represent a Ci to Ci2 alkyl group. The alkyl group may be straight chain, that is linear, or branched. The alkyl group has up to 12 carbon atoms, that is be a Ci, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12 alkyl group. -6 -

Each R may represent a phenyl group. The phenyl group may bear one or more substituents. Preferred substituents for the phenyl group are Ci to C4 alkyl groups, more preferably Ci to C3 alkyl groups, still more preferably Ci to C2 alkyl groups, with methyl being a preferred alkyl subtituent. The phenyl group may be substituted in one or more of the o-, m-or p-positions, with p-substituted phenyl being a preferred group for many embodiments.

Examples of preferred groups represented by R in the general formula I are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, isooctyl, decyl, dodecyl, phenyl, p-methylphenyl, and polysubstituted phenyl.

It is preferred that the group represented by each R is the same.

Preferably, the phosphite ester of general formula I is selected from trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, trihexyl phosphite, tri(2-ethylhexyl) phosphite, trioctyl phosphite, triisooctyl phosphite, triphenyl phosphite, tri-p-methylphenyl phosphite, and triethylphenyl phosphite.

The composition may comprise a single phosphite ester of the general formula I or a mixture of two or more phosphite esters of the general formula I. The phosphite ester of general formula I may be present in the emulsifiable concentrate (EC) composition in any suitable amount to provide the required stabilising effect. The phosphite ester may be present in the composition in an amount of up to 750 g/L, preferably up to 700 g/L, more preferably up to 650 g/L, still more preferably up to 600 g/L, more preferably still up to 550 g/L, especially up to 500 g/L, more especially up to 450 g/L, still more especially up to 400 g/L. The composition may comprise the phosphite ester in an amount of from 10 g/L, preferably from 25 g/L, more preferably from 50 g/L, still more preferably from 75 g/L, more preferably still from 100 g/L, especially from 125 g/L, more especially from 150 g/L. Preferred embodiments of the composition comprise the phosphite ester in an amount of from 10 to 700 g/L, more preferably from 50 to 600 g/L, still more preferably from 100 to 600 g/L, more preferably still from 100 to 500 g/L, and especially from 150 to 400 g/L. -7 -

The amount of cloquintocet-mexyl to be employed relative to the amount pinoxaden is determined by the amount required to provide the required safening effect. Combinations of pinoxaden and cloquintocet-mexyl are known in the art, including in emulsifiable concentrate (EC) formulations, as discussed hereinbefore.

In general, pinoxaden will be employed in a weight excess to the amount of cloquintocet-mexyl. The ratio of pinoxaden and cloquintocet-mexyl present in the emulsifiable concentrate (EC) formulation may be from 1:1.5 to 1:6, preferably from 1:2 to 1:5, more preferably from 1:2.5 to 1:4.5, especially from 1:2.5 to 1:4.

The phosphite ester of general formula (I) is present in the emulsifiable concentrate (EC) composition in an amount sufficient to stabilise both pinoxaden and cloquintocet-mexyl. The phosphite ester is preferably employed in a weight excess compared with the amount of pinoxaden in the composition. The weight ratio of the phosphite ester to pinoxaden may be from 2:1 to 25:1, more preferably from 2.5:1 to 20:1, still more preferably from 3:1 to 18:1, more preferably still from 3.5:1 to 15:1. The phosphite ester is preferably employed in a weight excess compared with the amount of cloquintocet-mexyl in the composition. The weight ratio of the phosphite ester to cloquintocet-mexyl may be from 10:1 to 45:1, more preferably from 12:1 to 40:1, still more preferably from 14:1 to 35:1, more preferably still from 15:1 to 30:1.

The emulsifiable concentrate (EC) composition further comprises one or more solvents. Suitable solvents are those that will dissolve both pinoxaden and cloquintocet-mexyl in the required amounts.

Preferred solvents include: ketones, such as cyclohexanone, acetophenone, butanone, methyl-n-amyl ketone, and methyl isobutyl ketone; amides, such as N,N-dimethyldecanamide, N,N-dimethyloctanamide, and N,Ndimethyldecenam ide; cyclic compounds, such as N-methyl-pyrrolidone, N-octylpyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactam, N-dodecyl-caprolactam, and y-butyrolactone; benzoate solvents, such as benzyl benzoate, methyl -8 -benzoate, and dipropylene glycol dibenzoate; lower alkyl esters of higher fatty acids, such as C8 to C10 fatty acid methyl esters and C16 to C18 fatty acid methyl esters; aromatic hydrocarbon solvents, for example, toluene, xylene, cumene, and blends of high boiling point aromatic distillates, for example the commercially available aromatic solvents Solvesso 100, Solvesso 150, and Solvesso 200 (commercially available from ExxonMobil); esters, such as propylene glycol monomethyl ether acetate, dibutyl adipate, ethyl acetate, heptyl acetate, tri-n-butyl citrate, and di-n-butyl phthalate; alcohols, such as straight chain or branched CI to C12 alkanols, for example methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, isobutanol, isoamyl alcohol, 2-ethylhexanol and isotridecanol; diols or triols, such as ethylene glycol, propylene glycol, 1-methoxy-2-dipropanol, dipropylene glycol ether, and 2-methyl-2,4-pentanediol; glycol monoethers, such as ethylene glycol butyl ether and diethylene glycol butyl ether; furfuryl and tetrahydrofurfuryl alcohols, benzyl alcohol, and 4-hydroxy-4-methyl-2-pentanone; esters, for example alkyl lactates, such as ethyl lactate and butyl lactate; and cyclic alcohols, such as cyclopentanol and cyclohexanol.

The solvent may be present in the emulsifiable concentrate (EC) composition in any suitable amount. The solvent may be present in the composition in an amount of up to 950 g/L, preferably up to 900 g/L, more preferably up to 850 g/L, still more preferably up to 800 g/L, more preferably still up to 750 g/L, especially up to 700 g/L, more especially up to 650 g/L, still more especially up to 600 g/L. The composition may comprise the solvent in an amount of from 1 g/L, preferably from 25 g/L, more preferably from 50 g/L, still more preferably from 100 g/L, more preferably still from 150 g/L, especially from 175 g/L, more especially from 200 g/L. Preferred embodiments of the composition comprise the solvent in an amount of from 1 to 900 g/L, more preferably from 100 to 800 g/L, still more preferably from 200 to 600 g/L.

The emulsifiable concentrate (EC) composition further comprises one or more emulsifiers. Suitable emulsifiers and their use for formulating EC formulations are known in the art. -9 -

Suitable emulsifiers include castor oil-alkylene oxide addition products (condensation products), particularly castor oil ethoxylates, which can for example have varying amounts of ethoxylation, such as castor oil ethoxylates (20 to 50 E0; i.e. containing 20 to 50 moles of ethylene oxide (E0) per mole of castor oil or produced therefrom) or preferably castor oil ethoxylates (30 to 44 E0); alcohol-alkylene oxide addition products (condensation products), particularly Ci to C22 alcohol-alkylene oxide addition products, such as C8 to C22 alcohol ethoxylates, which may for example have varying amounts of ethoxylation, such as tridecanol ethoxylate; alkylphenol-alkylene oxide addition products (condensation products), such as nonylphenol ethoxylates; sorbitol esters, such as sorbitan oleate; polyethylene glycol esters of C8 to C22 fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide (E0) and propylene oxide (PO); butanol ethylene oxide (E0)/propylene oxide (PO) copolymers and methyl ethylene oxide polymers with ethylene oxide and monobutyl ether, such as Atlas G5000DTM butanol EO/PO copolymers (for example, available from CRODA); salts of Ci to C22 alkyl-phenyl-sulfonates, for example alkaline earth metal salts, such as calcium salts, such as salts of Ca to Cie alkyl-phenyl-sulfonates, for example calcium dodecylbenzenesulfonate; di-Ci to C22 alkyl esters of sulfosuccinates, such as sodium bis(2-ethylhexyl)sulfosuccinate; and salts of mono-and/or di-alkyl phosphates; or mixtures of two or more of these emulsifiers.

Alternatively or additionally, one or more other emulsifiers may be used, preferably tristyrylphenol alkoxylates, such as tristyrylphenol ethoxylates and/or tristyrylphenol ethoxylate-propoxylates, more particularly tristyrylphenol ethoxylates containing 8 to 30 (preferably 10 to 25) moles of ethylene oxide (EO) per mole of tristyrylphenol, for example Soprophor TS/10Tm (10 moles of E0), Soprophor BSLJTM (16 moles of E0) or Soprophor S/2STM (25 moles of E0) (commercially available from Rhodia).

The emulsifier may be present in the emulsifiable concentrate (EC) composition in any suitable amount. The emulsifier may be present in the composition in an amount of up to 450 g/L, preferably up to 400 g/L, more -10 -preferably up to 350 g/L, still more preferably up to 300 g/L, more preferably still up to 250 g/L, especially up to 200 g/L, more especially up to 175 g/L, still more especially up to 150 g/L. The composition may comprise the emulsifier in an amount of from 1 g/L, preferably from 2 g/L, more preferably from 5 g/L, still more preferably from 10 g/L, more preferably still from 15 g/L, especially from 17 g/L, more especially from 20 g/L. Preferred embodiments of the composition comprise the emulsifier in an amount of from 1 to 300 g/L, more preferably from 10 to 200 g/L, still more preferably from 20 to 150 g/L.

The emulsifier is particularly preferably a castor oil-alkylene oxide addition product (condensation product), more preferably a castor oil ethoxylate, preferably having 20 to 50 E0 (that is containing 20 to 50 moles of ethylene oxide (E0) per mole of castor oil and/or produced therefrom), more preferably 30 to 44 E0. The castor oil-alkylene oxide addition product may be present in the composition in an amount of up to 250 g/L, preferably up to 225 g/L, more preferably up to 200 g/L, especially up to 180 g/L. The composition may comprise the castor oil-alkylene oxide addition product in an amount of from 10 g/L, preferably from 20 g/L, more preferably from 30. Preferred embodiments of the composition comprise the castor oil-alkylene oxide addition product in an amount of from 10 g/L to 150 g/L, preferably from 20 g/L to 100 g/L, and more preferably from 30 g/L to 80 g/L.

In addition to the herbicide pinoxaden, the emulsifiable concentrate (EC) composition of the present invention may contain one or more other herbicides which are compatible therewith. The term "compatible" as used herein means that the herbicidal composition is chemically stable and neither exhibits an antagonistic action nor increases the phytotoxicity of pinoxaden to useful plants.

Such further herbicides are preferably selected from sulfonylureas, such as triasulfuron, tribenuron, metsulfuron, thifensulfuron, flupyrsulfuron, chlorsulfuron, prosulfuron, am idosulfuron, mesosulfuron, sulfosulfuron and tritosulfuron; aryloxyphenoxypropionates and heteroaryloxyphenoxypropionates, such as clodinafop-propargyl, fenoxaprop-P-ethyl, diclofop-methyl and cyhalofop-butyl; triazolylpyrimidines, such as florasulam, metosulam and flumetsulam; arylcarboxylic acids, preferably dicamba and clopyralid; aryloxycarboxylic acids, preferably 2,4-D ester, 2,4-DP, mecoprop, mecoprop-P, MCPA, MCPB, dichlorprop-P and fluroxypyr; cyclohexanedione oximes, such as tralkoxydim; thiocarbamates, such as triallate and prosulfocarb; hydroxybenzonitriles, such as bromoxynil, bromoxynil octanoate, ioxynil and ioxynil octanoate; dinitroanilines, such as pendimethalin and trifluralin; and pyridinecarboxam ides, such as diflufenican.

The emulsifiable concentrate (EC) composition may optionally comprise one or more additional formulation auxiliaries known in the art, for example, crystallization inhibitors, viscosity modifying substances, suspending agents, dyes, antioxidants, defoamers, opacifiers, pH adjusters, colorants, wetting agents, synergists, micronutrients, dispersants, antifreeze agents, microbicides and fertilizers. Such formulation auxiliaries and their use are known in the art.

The emulsifiable concentrate (EC) composition of the present invention may be prepared using techniques known in the art for preparing EC formulations. In general, the emulsifiable concentrate (EC) composition may be prepared by combining: (1) pinoxaden; (2) cloquintocet-mexyl; (3) a phosphite ester having a general formula (I): wherein each R is independently a Ci to C12 alkyl group or a phenyl group; -12 - (4) at least one solvent, and (5) at least one emulsifier.

For example, one or more phosphite esters and one or more solvents may be added to a compounding vessel, such as a compounding kettle with hot water circulation. Preferably the mixture is stirred. Pinoxaden, cloquintocet-mexyl and any other herbicides to be included in the EC formulation may then be added to the compounding vessel. Stirring may be continued until all the components are completely dissolved. Thereafter, additional formulating agents, such as the emulsifier may be added, and stirring continued until complete homogeneity of the mixture is achieved.

Still further, the present invention provides a method for controlling unwanted plant growth, the method comprising applying to the plant or a growing environment thereof an emulsifiable concentrate (EC) composition as hereinbefore described.

In a further aspect, the present invention provides the use of an emulsifiable concentrate (EC) formulation as hereinbefore described in the control of unwanted plant growth.

Techniques for applying emulsifiable concentrate (EC) compositions are known in the art. In general, the emulsifiable concentrate (EC) composition is preferably diluted with water to form a dispersion, after which the dispersion is applied to the plants to be protected, the unwanted plant growth and/or their locus. Suitable techniques for applying the dispersion are known in the art and include spraying.

The emulsifiable concentrate (EC) composition of the present invention is advantageously used to protect useful plants, such as crop plants, in particular by -13 -preventing unwanted plant growth in the crops or their locus. The emulsifiable concentrate (EC) composition is useful for the protection of crops such as cereals, cotton, soybeans, sugar beets, sugar cane, plantation plants, oilseed rape, maize and rice. The emulsifiable concentrate (EC) composition is especially useful for the protection of corn and cereal crops. The emulsifiable concentrate (EC) composition is more especially advantageous in the protection of crops of grains, in particular wheat, triticale, rye and barley crops. The emulsifiable concentrate (EC) composition is effective in the non-selective control of weeds.

The emulsifiable concentrate (EC) composition is effective in the control of the growth of a range of unwanted plants. The unwanted plants may be monocotyledonous and/or dicotyledonous weeds. Examples are the genera Stellaria, Apera, Avena, Setaria, Sinapis, Lolium, Echinochloa, Bromus, Alopecurus, Phalaris, Amaranthus, Chenopodium, Convolvulus, Chrysanthemum, Papaver, Cirsium, Polygonum, Matricaria, Galium, Viola, and Veronica.

As discussed hereinbefore, it has been found that phosphite esters of the general formula (I) as hereinbefore defined are effective in stabilising both pinoxaden and cloquintocet-mexyl in emulsifiable concentrate (EC) formulations.

Therefore, in a further aspect, the present invention provides the use of a phosphite ester having a general formula (I): Fonnul wherein each R is independently a Ci to Ci2 alkyl group or a phenyl group; -14 -for improving the stability of pinoxaden in an emulsifiable concentrate (EC) composition.

In a still further aspect, the present invention provides the use of a phosphite ester having a general formula (I): wherein each R is independently a Ci to C12 alkyl group or a phenyl group; for improving the stability of cloquintocet-mexyl in an emulsifiable concentrate (EC) composition.

In a still further aspect, the present invention provides a method of increasing the stability of pinoxaden in an emulsifiable concentrate (EC) composition, the method comprising including in the composition a a phosphite ester having a general formula (I): Forinula wherein each R is independently a Ci to Ci2 alkyl group or a phenyl group.

In a still further aspect, the present invention provides a method of increasing the stability of cloquintocet-mexyl in an emulsifiable concentrate (EC) composition, the method comprising including in the composition a a phosphite ester having a general formula (I): Formula -15 -wherein each R is independently a Ci to C12 alkyl group or a phenyl group.

As described hereinbefore, the use of the phosphite ester of general formula (I) as hereinbefore defined is particularly advantageous in improving the stability of both pinoxaden and cloquintocet-mexyl when both are present in an emulsifiable concentrate (EC) composition.

Aspects of the present invention will be further described by way of the following working examples, which are provided purely for illustrative purposes.

In the following examples, percentages are % by weight, unless otherwise indicated.

EXAMPLES Example 1

An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden 50 g Cloquintocet-mexyl 12.5 g -16 -Triethyl phosphite 300 g Castor oil ethoxylate (30E0) 30 g Butanol polyoxyethylene polyoxypropylene block copolymer 20 g SOLVESSO 2000ND making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Example 2

An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden 80 g Cloquintocet-mexyl 30 g Triphenyl phosphite 350 g Calcium dodecyl sulfate salt 20 g Castor oil ethoxylate (20E0) 50 g Tetrahydrofurfuryl alcohol 200 g SOLVESSO 2000ND making up to 1 L -17 -The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Example 3

An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden Cloquintocet-mexyl Tri(2-ethylhexyl) phosphite Calcium dodecyl sulfate salt Tristyrylphenyl polyoxyethylene ether Tri-(2-ethylhexyl) phosphate Tetrahydrofurfuryl alcohol SOLVESSO 200®ND g g 250 g g g 300 g g making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Example 4

An emulsifiable concentrate (EC) composition was prepared from the following components: -18 -Pinoxaden 50 g Cloquintocet-mexyl 12.5 g Triphenyl phosphite 250 g Tristyrylphenol polyoxyethylene ether 80 g Ethylene oxide propylene oxide monononylphenol ether 20 g N-methylpyrrolidone 100 g Propylene carbonate 100 g Acetophenone 100 g SOLVESSO 200 ND making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Example 5

An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden 50 g Cloquintocet-mexyl 12.5 g Tributyl phosphite 280 g Castor oil ethoxylate 30 g -19 -Calcium dodecylbenzenesulfonate 2-Methyl-2,4-pentanediol 30 g 300 g 200 g Triethyl phosphate SOLVESS0100°N D making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Example 6

An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden Cloquintocet-mexyl Triisopropyl phosphite Castor oil ethoxylate Calcium dodecylbenzenesulfonate N,N-dimethyldecanamide Methyl oleate 60 g 15 g 400 g 30 g 30 g 300 g making up to 1 L -20 -The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Comparative Example Cl An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden 50 g Cloquintocet-mexyl 12.5 g Castor oil ethoxylate (30E0) 30 g Butanol polyoxyethylene polyoxypropylene block copolymer 20 g SOLVESSO 200OND making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Comparative Example C2 An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden 80g Cloquintocet-mexyl 30 g -21 -Calcium dodecyl sulfate salt Castor oil ethoxylate (20E0) Tetrahydrofurfuryl alcohol SOLVESSO 2000ND 20 g 50 g 200 g making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Comparative Example C3 An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden Cloquintocet-mexyl Calcium dodecyl sulfate salt Tristyrylphenyl polyoxyethylene ether Tri-(2-ethylhexyl) phosphate Tetrahydrofurfuryl alcohol SOLVESSO 2000ND g 5g g g 300 g g making up to 1 L -22 -The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Comparative Example C4 An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden 50 g Cloquintocet-mexyl 12.5 g Tristyrylphenol polyoxyethylene ether 80 g Ethylene oxide propylene oxide monononylphenol ether 20 g N-methylpyrrolidone 100 g Propylene carbonate 100 g Acetophenone 100 g SOLVESSO 200®ND making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Comparative Example C5 An emulsifiable concentrate (EC) composition was prepared from the following components: -23 -Pinoxaden 50g Cloquintocet-mexyl 12.5 g Castor oil ethoxylate 30 g Calcium dodecylbenzenesulfonate 30 g 2-Methyl-2,4-pentanediol 300 g Triethyl phosphate 200 g SOLVESS0100 ND making up to 1 L The components indicated above were combined in a vessel and stirred until a clear solution was obtained.

Comparative Example C6 An emulsifiable concentrate (EC) composition was prepared from the following components: Pinoxaden 60 g Cloquintocet-mexyl 15 g Castor oil ethoxylate 30 g Calcium dodecylbenzenesulfonate 30 g N, N-dimethyldecanam ide 300 g Methyl oleate making up to 1 L -24 -Thermal Storage Stability Test Samples of the compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were stored in an oven at 54°C for 2 weeks. The amount (g/L) of pinoxaden and cloquintocet-mexyl present in the composition both before and after storage 5 were measured and the loss (%) was calculated.

The results are shown in Table 1 below.

Table 1

Example Pinoxaden Cloquintocet-mexyl No. Content Content Degradation Content Content Degradation before after (0A) before after (%) storage storage storage storage (g/L) (g/L) (g/L) (g/L) 1 50.12 47.83 4.57 12.55 11.96 4.70 2 80.52 78.31 2.74 30.02 28.97 3.50 3 20.18 19.88 1.49 5.05 4.85 3.96 4 50.29 48.25 4.06 12.53 11.99 4.31 49.98 49.05 1.86 12.58 12.16 3.34 6 60.32 57.78 4.21 15.16 14.45 4.68 Cl 50.18 40.32 19.65 12.52 10.38 17.09 8E91- 911Z k 96171 99.81. 1:6fr 1-£.09 90 Z17.6 17£.1. k ZS.ZI 6£Z 90.6P 9Z.09 90 960k 1-9.31 6E.Z1 £0.9fr 2009. t 0 60* 39.9 99* 66* 9.3 E9.61- 96.61- E 0 30.01 1.313 173.0£ L9.£ 92.11 1-2.09 33 -93 -The data set out in Table 1 above show that the emusifiable concentrate (EC) compositions of the present invention that comprise a phosphite ester of the general formula (I) as hereinbefore defined exhibit a significantly increased stability of each of pinoxaden and cloquintocet-mexyl, compared with the corresponding formulations prepared without a phosphite ester. The comparative formulations Cl to C6 exhibited a low stability for pinoxaden and, in particular, cloquintocet-mexyl. It is significant that the phosphite ester acts to increase the stability of both components in the EC formulation.

Claims

-28 -CLAIMS1. A herbicidal composition in the form of an emulsifiable concentrate (EC), the herbicidal composition comprising: (1) pinoxaden; (2) cloquintocet-mexyl; (3) a phosphite ester having a general formula (I): Formula wherein each R is independently a Ci to C12 alkyl group or a phenyl group; (4) at least one solvent; and (5) at least one emulsifier.
2. The composition according to claim 1, wherein pinoxaden is present in the composition in an amount of from 1 to 200 g/L.
3. The composition according to claim 2, wherein pinoxaden is present in the composition in an amount of from 10 to 100 g/L.
-29 - 4. The composition according to any preceding claim, wherein cloquintocet-mexyl is present in the composition in an amount of from 0.5 to 50 g/L.
5. The composition according to claim 4, wherein cloquintocet-mexyl is present in the composition in an amount of from ito 25 g/L.
6. The composition according to any preceding claim, wherein each R in the phosphite ester of general formula (I) is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, phenyl, and
7. The composition according to claim 6, wherein the phosphite ester of general formula (I) is selected from triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, trihexyl phosphite, trioctyl phosphite, tri- (2-ethyl-hexyl) phosphite, tri-dodecyl sulfate phosphite, triphenyl phosphite, and tri-p-methylphenyl phosphite.
8. The composition according to any preceding claim, wherein the phosphite ester is present in the composition in an amount of from 50 to 600 g/L.
9. The composition according to claim 8, wherein the phosphite ester is present in the composition in an amount of from 100 to 500 g/L.
10. The composition according to any preceding claim, wherein the weight ratio of the phosphite ester to pinoxaden is from 2:1 to 25:1.
11. The composition according to any preceding claim, wherein the weight ratio of the phosphite ester to cloquintocet-mexyl is from 10:1 to 45:1.
12. The composition according to any preceding claim, wherein the solvent is selected from aromatic hydrocarbons, alcohols, ketones, amides, esters and mixtures thereof.
13. The composition according to claim 12, wherein the solvent comprises an aromatic hydrocarbon selected from toluene, xylene, cumene and blends of high boiling aromatic hydrocarbons.
14. The composition according to claim 12, wherein the solvent comprises an alcohol selected from propanol, hexanol, octanol, dodecanol, 2-ethylhexanol, isotridecanol, dipropylene glycol ether, 2-methyl-2,4-pentanediol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, 4-hydroxy-4-methyl-2-pentanone, cyclopentanol, cyclohexanol, and mixtures thereof.
15. The composition according to claim 12, wherein the solvent comprises a ketone selected from cyclohexanone, acetophenone, butanone, methyl-n-amyl ketone, methyl isobutyl ketone, N-methylpyrrolidone and mixtures thereof.
16. The composition according to claim 12, wherein the solvent comprises an amide selected from N,N-dimethyldecanamide, N,N-dimethyloctanamide, and N,N-dimethyldecenamide and mixtures thereof.
17. The composition according to claim 12, wherein the solvent comprises an ester selected from propylene carbonate, y-butyrolactone, butyl lactate, ethyl lactate and mixtures thereof.
18. The composition according to any preceding claim, wherein the emulsifier comprises an alkyl sulfonate, a vegetable oil alkoxylate, an alkylphenol epoxide, an ethylene oxide and propylene oxide block copolymer or a mixture thereof.
19. The composition according to any preceding claim comprising: (1) 10 to 100 g/L of pinoxaden; (2) 1 to 25 g/L of cloquintocet-mexyl; (3) 100 to 500 g/L of a phosphite ester having a general formula (I): f FOI 1_ a wherein each R is independently a Ci to C12 alkyl group or a phenyl group; (4) 100 to 800 g/L of at least one solvent, and (5) 1 to 200 g/L of at least one emulsifier.
20. A method of controlling unwanted plant growth comprising applying to the plants or their locus a composition according to any preceding claim.
21. Use of a composition according to any of claims 1 to 19 in the control of unwanted plant growth.
22. Use of a phosphite ester having a general formula (I): wherein each R is independently a Ci to C12 alkyl group or a phenyl group; for improving the stability of pinoxaden in an emulsifiable concentrate (EC) composition.
23. Use of a phosphite ester having a general formula (I): Formula t wherein each R is independently a Ci to C12 alkyl group or a phenyl group; -33 -for improving the stability of cloquintocet-mexyl in an emulsifiable concentrate (EC) composition.
24. A method of increasing the stability of pinoxaden in an emulsifiable concentrate (EC) composition, the method comprising including in the composition a a phosphite ester having a general formula (I): Formula wherein each R is independently a Ci to C12 alkyl group or a phenyl group.
25. A method of increasing the stability of cloquintocet-mexyl in an emulsifiable concentrate (EC) composition, the method comprising including in the composition a a phosphite ester having a general formula (I): wherein each R is independently a CI to C12 alkyl group or a phenyl group.