SK21894A3 - Herbicidal mixture comprising triazole derivative and sulphonylureas herbicide - Google Patents

Abstract

The solution relates to a composition comprising) a triazole compound of formula I wherein R is an unbranched alkyl group C 1 -C 10, unsubstituted or substituted with 1 to 19 fluorine atoms, a branched alkyl group with 3 to 10 carbon atoms, unsubstituted or substituted with 1 to 19 fluorine atoms, cyclic alkyl with 3 to 10 carbon atoms, alkyl having 1 to 3 carbon atoms; carbon atoms substituted with an alicyclic structure having 3 to 7 carbon atoms, phenyl or aralkyl having 7 to 7 carbon atoms; 9 carbon atoms; X 1 is halogen or alkyl having 1 to 1 3 carbon atoms; X 2 is hydrogen, halogen or alkyl C 1 -C 3; Y 1 is hydrogen or fluoro and Y 2 is hydrogen or fluorine. Further, the composition comprises at least one coherbicide selected from sulfonylurea herbicides.

Description

A herbicidal mixture comprising a triazole derivative and a sulfonic acid urea herbicide

Technical field

The invention relates to herbicidal mixtures or combinations comprising triazole derivatives known and described in EP-0 282 303 and at least one sulfonylurea herbicide.

BACKGROUND OF THE INVENTION

EP-0 282 303 describes 1,5-diphenyl-1H-1,2,4-triazole-5-carboxamide derivatives of the general formula I

wherein R is a C 1 -C 10 alkyl, unsubstituted or substituted by 1 to 19 fluorine atoms, a C 3 -C 10 branched alkyl, unsubstituted or substituted by 1 to 19 fluorine atoms, a C 3 -C 10 cyclic alkyl group, (C 1 -C 3) substituted by a (C 3 -C 7) cyclic structure; (C 7 -C 9) phenyl or aralkyl; X ¹ is halogen or C 1 -C 3 alkyl; X ³ is hydrogen, halogen or C 1 -C 3 alkyl; Y ¹ is hydrogen or fluoro and Y ² is hydrogen or fluoro. Said derivatives and mixtures containing them have a high pre-emergence and post-emergence herbicidal effect, but are practically harmless to rice, wheat and corn.

The disadvantage of these derivatives is that they are not equally effective on all weed species that are practically present. More specifically, weeds such as geranium, matricaria and brassica are not readily suppressible by said derivatives unless they are used in relatively high amounts. A high dose of these derivatives may damage crops such as cereals, but is not limited to rice, wheat and corn, but reduces the commercial interest in these derivatives.

It is known to solve problems of this kind by combining herbicides. Such combinations, however, are intended to have good properties of major herbicides, in this case triazole derivatives; there is little interest in antagonist combinations. Obviously, it has been difficult to determine the efficacy of the composition in terms of the amount of herbicides available.

EP-0 182 740 discloses a herbicidal mixture of triazole derivatives of the formula

CONH 3 and a herbicidal urea, sulfonylurea or triazine derivative. Said compositions have a synergistic herbicidal action against most monocotyledonous and dicotyledonous weeds found in agricultural crops.

Before EP-0 282 303, herbicidal mixtures containing isoproturon (a urea herbicide) and a triazole derivative in the weight ratio triazole: isoproturon derivative from 3: 1 to 1:50 have been described in EP EP-0 427 695. The mixture had a high degree of phytotoxicity at low levels of the triazole derivative in pre-emergence and post-emergence applications.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention is based on the preparation of novel and herbicidally active mixtures or combinations containing said triazole derivative of the formula (I).

Further, the essence is to provide a herbicidally active composition or combination that is more effective against a broad spectrum of weeds than any active ingredient per se.

The present invention further provides an improved herbicidally active composition or combination that is effective against a broad spectrum of weeds, such as said triazole derivative, and retains its selective crop properties upon post-emergence application.

According to a further aspect of the present invention, the principle consists in a method of controlling and suppressing germination and growth ^with undesirable vegetation, such as rice, wheat and maize.

Surprisingly, it has been found that mixtures of said triazole derivatives with a sulfonylurea herbicide are particularly effective on a broad spectrum of weeds and moreover have a synergistic effect.

The present invention relates to novel herbicidal compositions comprising a triazole derivative of the formula I

Nn — CNH ₂

Y ¹

Y ²

wherein R is a C 1 -C 10 alkyl, unsubstituted or substituted by 1 to 19 fluorine atoms, a C 3 -C 10 branched alkyl, unsubstituted or substituted by 1 to 19 fluorine atoms, a C 3 -C 10 cyclic alkyl group, (C 1 -C 3) substituted with an alicyclic structure of up to 7 carbon atoms, phenyl or aralkyl of 7 to 9 carbon atoms; X ¹ is halogen or C 1 -C 3 alkyl; X ² is hydrogen, halogen or C 1 -C 3 alkyl; Y ¹ is hydrogen or fluorine fluorine and at least one coherbicide selected and Y ² is hydrogen or from sulfonylurea herbicides.

It has been found that mixtures herbicidal activity in the herbicide, because they lack weak weeds,

In addition, they are effective, in accordance with the invention, to have improved triazole activity against those species which are difficult to destroy by the triazole derivatives alone. the spectrum of weeds on which the compositions of the invention are present is broader compared to the triazole herbicide alone.

It is also surprising that the compositions of the present invention do not simply have an additive herbicidal effect on most weeds substantially widespread in monocotyledonous crops, but have a synergistic effect.

As a result, the amount of individual herbicide applied is lower, while the efficacy is maintained at the same level. In addition, the combination shows an acceptable degree of weed activity even when each of the herbicides has become ineffective due to the low application rate. This means increasing the margin of safety for suboptimal applications.

According to an exemplary embodiment of the invention, the triazole derivative has the formula I wherein X ¹ is chlorine, X ² is hydrogen, Y ¹ and Y ² are hydrogen and R is -CF 2 CF 3.

Both sulfonylureas and novel herbicides are known and other derivatives are being developed. The effect of sulfonylurea herbicides is generally known as yellowing of the whole plant. Preferred sulfonylurea herbicides are metsulfuron-methyl, chlorosulfuron, triasulfuron or thifensulfuron, tribenuron, renriduron, nicosulfuron and amidosulfuron.

Particularly preferred mixtures are the triazole derivative of the formula I wherein X ¹ is chlorine, X ² is hydrogen, Y ¹ and Y ^{2 are} hydrogen and R is -CF ² CF 3, in combination with metsulfuron-methyl or triasu1 furone.

The compositions of the invention may contain the triazole derivative and the sulfonylurea herbicide in any ratio, depending on the conditions of application and the type of herbicides used in the composition.

In the case of a mixture of preferred methylsulfuron-methyl, it is preferred that it is (triazole derivative: coherbicide). .

a triazole derivative and a ratio of from 250: 1 to 15: 1

In the case of triasulfuron (the triazole derivative of the mixture of the preferred derivative is preferred if the ratio is from a coherbicide).

triazole and 250: 1 to 15: 1

According to another embodiment of the invention, it is preferred that the combinations comprise the preferred triazole derivative mentioned above and a mixture of two or more of said coherbicides.

When looking at another aspect, it is also an object of the present invention to use the above compositions for selectively killing or inhibiting the growth or germination of unwanted plants by sequential or simultaneous application to plants, seeds or seed or plant sites.

DETAILED DESCRIPTION OF THE INVENTION

It will be appreciated that the individual components of the composition as defined above may be applied to seeds, plants or seed or plant destinations simultaneously or sequentially. Simultaneous application is preferred. In this case, the mixture may be applied in the form of a tank mix of the individual herbicidal components, with the possibility of adding agriculturally known adjuvants such as surfactants, antifreeze agents and the like, in the form of a finely divided powder mixture of triazole derivative and co-herbicide. ready-to-use mixtures containing said herbicidal components supplemented with adjuvants, surfactants, etc., or in the form of a solution, dispersion or emulsion concentrate or even a solid product, again containing the herbicidal components, adjuvants or other agriculturally known adjuvants. The application rates depend on the particular conditions of use and the particular herbicidal mixture.

Herbicidal mixtures containing a triazole derivative and co-herbicides as well as formulations derived therefrom, including aqueous or anhydrous solution concentrates and aqueous suspensions which require dilution prior to use, are all exemplary embodiments of the present invention and are referred to as term mixtures. The compositions may contain herbicidally active ingredients mixed in a ratio of from 0.1 to 100% by weight. and may also contain at least one agriculturally acceptable adjuvant in liquid or solid form. The herbicidal components may be present in the compositions as free or in the form of an agriculturally acceptable acid salt, complex or association product, such as e.g. a complex or association product formed by metal ions.

The mixtures are prepared by known technological processes by mixing the herbicidally active ingredients with one or more adjuvants, including diluents, fillers, carriers and conditioning agents, to form mixtures in the form of finely divided solids, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredients may be used with an adjuvant as a finely divided solid, an emulsifying agent (emulsifier), a stabilizing agent (stabilizer), an antifreeze agent, an antifoam, or any suitable combination thereof.

Suitable surfactants are alkylbenzenesulfonates, alkylnaphthalenesulfonates, sulfonated fatty alcohols, amines or amino acids, higher sodium isothionate esters, sodium sulfomaleinate esters, sulfonate or sulfonate fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, polyetherlyl phenoxy acetylenes, di-tertiaryl phenol sulfenates and nonylphenol) and polyoxyethylene derivatives of higher fatty acid monoesters hexitolanhydrides (e.g. sorbitol), alkoxylated amines, inorganic ammonium salts such as ammonium sulfate, ammonium nitrate and ammonium phosphates, ammonium salts derived from organic amino acids such as primary, secondary and tertiary amines, Ethylenediamine morpholine, polyamines, alkoxylated amines and Preferred dispersing agents are polyvinyl alcohol, sodium lignosulfonate, alkylnaphthalenesulfonate, naphthalenesulfonate bis-naphthalenes lfónan.

and piperazine, aminotensides. methylcellulose, polymers and sodium polymethylene

Wettable powders are water-dispersed mixtures comprising a mixture of active ingredients, an inert solid filler and one or more wetting and dispersing agents. Inert solid fillers are usually of mineral origin, such as natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such fillers are. kaolins, attapulgite and synthetic magnesium silicates. The wettable powder compositions of the invention typically comprise from 0.5 to 60 parts (preferably 5 to 20 parts) of a mixture of active ingredients, from 0.25 to 25 parts (preferably 1 to 15 parts) of a wetting agent, 0.25 to 25 parts (a. preferably 1 to 15 parts) of a dispersant and 5 to 95 parts (preferably 5 to 50 parts) of an inert solid filler. wherein all parts are —worthy parts — of the total mixture. If desired, 0.1 to 2.0 parts of a solid inert filler may be replaced by a corrosion inhibitor or a defoamer, or both.

The compositions also contain powder concentrates consisting of 0.1 to 60% by weight. mixtures of the active ingredients on a suitable filler; these powder concentrates may be diluted to a concentration in the range of 0.1 to 10% by weight prior to application.

Compositions that are aqueous suspensions or emulsions can be prepared by mixing an anhydrous solution of the mixture of water-insoluble active ingredients and emulsifier with water into a uniform mixture and then homogenizing it to form an emulsion of finely divided particles. The resulting aqueous suspension concentration has extremely small particles, so that when diluted and sprayed, the coating is monolithic. Suitable concentrations of these dosage forms contain 0.1 to 60%, preferably 5 to 50% by weight. mixtures of active ingredients, up to a value given by the solubility limit of the active ingredients in solution.

Concentrates are usually solutions of a mixture of the active ingredients in solvents which are not mixed with water, partially mixed or mixed, together with a surfactant. Suitable solvents (diluents) of the active ingredients according to the invention are dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, amines and water-immiscible ethers, esters or ketones. However, other high performance liquid concentrates may be made by dissolving the active ingredient in a solvent and then diluting, e.g., kerosene, to a spray concentration.

Generally, the concentrates of the compositions comprise 0.1 to 95 parts (preferably 5 to 60 parts) of the active ingredient mixture, 0.25 to 50 parts (preferably 1 to 25 parts) of the surfactant and, if desired, 4 to 94 parts. parts of the solvent, based on the total weight of the emulsifying oil.

The compositions of the invention may also be in the form of granules, which are physically stable particle mixtures containing mixtures of the active ingredients, deposited on the matrix of inert finely divided filler particles, or distributed in the filler. In order to facilitate the release of the active ingredient from the particle, a surfactant from the group already mentioned may be used. Natural clays, pyrophyllites, ilite and vermiculite are examples of useful mineral fillers. Preferred fillers are porous, absorbent, preformed particles such as preformed and screened attapulgite or thermally expanded vermiculite and finely dispersed clays such as kaolin clays, hydrated attapulgite or bentonite clays.

These fillers are sprayed or mixed with the active ingredient to form herbicidal granules.

The granular compositions of the invention may contain 0.1 to 30 parts by weight. mixtures of active ingredients per 100 parts by weight. clay and 0 to 5 parts by weight. of a surfactant component per 100 parts by weight. clay particles (clay particles).

The compositions of the invention may also contain other additives, for example fertilizers, other herbicides, other pesticides, preservatives and other additives generally used in herbicidal formulations, used as an adjuvant or in combination with any of said adjuvants.

Suitable surfactants may be selected from Mc. Cutcheon's Detergents and Emulsifiers Yearbook, Mc Publishing Corp., Ridgewood, New Jersey, or equivalent technical documents.

It is generally accepted that, in the case of synergism, the efficacy of a mixture cannot be calculated from the effects of its individual components. Synergism is generally defined as the interaction of two or more compounds in which the overall organism response to the pesticide mixture is greater than the sum of the individual components.

A simple mathematical method for testing the additivity of a pesticidal composition is relationship based

Y (100-X)

E = X + ---------- 100 where X and Y represent the percent inhibition of growth by toxic substance A respectively. B, E is the expected percentage of growth inhibition by A + B. In order to demonstrate synergism, the actual efficacy should be higher than E.

EXAMPLE

The triazole compound of formula I wherein X ¹ is chlorine, X ² is hydrogen, Y ^x and Y ² are hydrogen and R is -CF 2 CF 3 is hereinafter referred to as Compound A, formulated as a suspension concentrate (SC) and containing about 42 % wt. active ingredient.

Compound A was tested in combination with various co-herbicides in a growth chamber.

The various co-herbicides used in the test are:

AM8ER (trade name): wettable granules containing 75% by weight. triasulfuron

ALLY (trade name): wettable granules containing% by weight. metsulturon-methyl.

Three sets of treatment vessels were randomly distributed in the growth chamber. Plants were treated about 3 weeks after planting. The plants were exposed to a photoperiod for 14 h daily; the temperature was 15 ° C during the day and 9 ° C at night. All applications were done with a MAR0RIVE sprayer, mimicking as much as possible the field conditions, sprayed at a pressure of 2 bar with a water volume of 200 l / ha.

The treated plants and the stage of their true leaves at spraying were as follows:

TRZAW winter wheat STEME Stellaria media leaves 6 leaves

LAMP Lamium perpureum 4 foliage MATCH Matricaria chamomilla 0-2 foliage GERMO Geranium molie 6 leaves 8RSNW winter oilseed rape 4 1 sure VERPE Veronica persica 4 foliage

The evaluation of the percentage of phytotoxicity was made by comparison with untreated control vessels on any scale from 1 to 100%, where 0 means no visible effect and 100 means the death of all plants. The results in Table 1 below represent the mean of three replicates.

The evaluation of the results table clearly shows that the compositions according to the invention show synergism while still maintaining the selectivity of herbicide A e.g. against winter wheat.

An example is a mixture of 62.5 g a.i./ha of Compound A and 1 g a.i./ha AMBER, which causes 95% suppression of the LAMP, while the expected suppression according to the above formula should be only 52%. 4 g of AMBER would be required to achieve 90% suppression and 4 times more compound A (250 g) gave only 40% suppression.

When the herbicide doses are further increased, the synergism is usually no longer so pronounced, since the percentage of growth inhibition is close to 100, which means complete death (destruction).

The unexpected synergistic phenomenon of the mixture represents an important technological contribution in the treatment of cereals. The range of action or spectrum of action is extended. In addition, lower amounts of herbicides may be used to achieve the effect each component provides per se.

Table 1

Dose ai g / ha TRZAW 14 DAT LAMP 14 DAT VERPE 14 DAT GERMO 14 DAT STEME 14 DAT BRSNW 14 DAT MATCH 14 DAT UNTRT.CHK 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 A 62.5 0.0 20.0 20.0 0.0 0.0 0.0 10.0 A 125 0.0 20.0 20.0 10.0 30.0 10.0 10.0 A 250 0.0 40.0 50.0 20.0 ^; 60.0 40.0 10.0

AMBER 1 0.0 40.0 10.0 10.0 40.0 10.0 50.0 AMBER 2 0.0 60.0 20.0 20.0 50.0 30.0 70.0 AMBER 4 0.0 90.0 30.0 20.0 80.0 70.0 85.0

A + 62.5 0.0 95.0 30.0 20.0 50.0 60.0 70.0 AMBER 1 A + 62.5 0.0 95.0 50.0 20.0 60.0 90.0 90.0 AMBER 2 A + 62.5 0.0 95.0 50.0 20.0 70.0 90.0 90.0 AMBER 4 A + 125 0.0 90.0 40.0 20.0 80.0 80.0 70.0 AMBER 1 A + 125 0.0 95.0 60.0 20.0 80.0 80.0 90.0 AMBER 2 A + 125 0.0 95.0 70.0 20.0 90.0 90.0 95.0 AMBER 4 A + 250 0.0 95.0 60.0 20.0 70.0 80.0 70.0 AMBER 1 A + 250 0.0 95.0 70.0 20.0 80.0 90.0 95.0 AMBER 2 A 4- 250 0.0 98.0 80.0 20.0 90.0 95.0 98.0 AMBER 4

11

Table 1 - continued

Dose ai g / ha TRZAW DAT 14 LAMPU VERPE GERMO STEME BRSNW 14 MATCH 14 14 14 ¹⁴ 14 ALLY 1 0.0 50.0 60.0 30.0 50.0 0.0 40.0 ALLY 2 0.0 70.0 70.0 40.0 60.0 30.0 60.0 ALLY 4 0.0 90.0 80.0 60.0 70.0 70.0 80.0 A + 62.5 0.0 80.0 80.0 50.0 70.0 20.0 90.0 ALLY 1 A + 62.5 0.0 80.0 90.0 60.0 80.0 40.0 95.0 ALLY 2 A + 62.5 0.0 95.0 95.0 90.0 90.0 95.0 98.0 ALLY 4 A + 125 0.0 95.0 98.0 50.0 80.0 70.0 85.0 ALLY 1 A + 125 0.0 95.0 95.0 80.0 80.0 95.0 98.0 ALLY 2 A + 125 0.0 98.0 98.0 90.0 90.0 95.0 95.0 ALLY 4 A + 250 0.0 90.0 98.0 80.0 90.0 80.0 90.0 ALLY 1 A + 250 0.0 95.0 98.0 90.0 95.0 95.0 95.0 ALLY 2 If 250 0.0 98.0 100.0 95.0 100.0 98.0 98.0

ALLY 4

Claims (5)

PATENT CLAIMS A composition comprising a triazole compound of formula I ABOUT N '• CNH Y * Y ² wherein R is a C 1 -C 10 alkyl, unsubstituted or substituted by 1 to 19 fluorine atoms, a C 3 -C 10 branched alkyl, unsubstituted or substituted by 1 to 19 fluorine atoms, a C 3 -C 10 cyclic alkyl group, (C 1 -C 3) alkyl substituted with (C 3 -C 7) alicyclic, (C 7 -C 9) phenyl or aralkyl; X ¹ is halogen or C 1 -C 3 alkyl; X ² is hydrogen, halogen or C 1 -C 3 alkyl; Y ¹ is hydrogen or fluoro and Y ² is hydrogen or fluoro and at least one coherbicide selected from sulfonylurea herbicides. A composition according to claim 1, wherein the triazole derivative is a compound of formula I wherein X ¹ is chlorine, X ² is hydrogen, Y ¹ and Y ² are hydrogen and R is -CF 2 CF 3. Mixture according to claim 1 or 2, characterized in that the sulfonylurea sulfuron-methyl, chlorosulfuron, characterized by the herbicide is preferably mettriasulfuron, thifensulfuron, tribenuron, renriduron, nicosulfuron or amidosulfuron. concentrate containing Herbicidal emulsion, in the form of a solution, dispersion or mixture according to any one of the preceding claims, and optionally containing adjuvants and agriculturally acceptable adjuvants, such as surfactants, antifreeze agents. A herbicidal spray solution comprising a composition according to claims 1 to 3a optionally containing an agriculturally acceptable adjuvant, as a surfactant, antifreeze agent. Use of a composition according to claims 1 to 3 for selectively controlling or inhibiting the growth or germination of unwanted vegetation by simultaneous application of a herbicidally effective amount of its components to plants, seeds or to a seed or plant planting site.