SK21694A3 - Herbicidal mixture comprising triazole derivative and diphenilether - Google Patents

Abstract

The present invention relates to a composition comprising a triazine compound of formula I wherein R is an unbranched alkyl group with 1 to 10 carbon atoms unsubstituted or substituted with 1 to 19 fluorine atoms, a branched alkyl group with 3 to 10 carbon atoms unsubstituted or substituted with I to. 19 fluorine atoms, cyclic an alkyl group having 3 to. With 10 carbon atoms, alkyl with I until. 3 carbon atoms substituted by an alicyclic structure with 3 to 7 carbon atoms, phenyl or aralkyl C 7 -C 9; X! is halogen or C 1 -C 3 alkyl; X 2 is hydrogen, halogen or an alkyl group up to. 3 carbon atoms; Y 1 is hydrogen or fluoro and Y 2 is hydrogen or fluoro. Next mix it comprises at least one coherbieid selected from the group of herbicides dilenyller type.

Description

A herbicidal mixture comprising a triazole derivative and diphenyl ether

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 diphenylether herbicide.

BACKGROUND OF THE INVENTION

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

wherein R is not, branched alkyl of 1 to 10 carbon atoms, unsubstituted or substituted with 1 to 19 fluorine atoms, branched alkyl of 3 to 10 carbon atoms, unsubstituted or substituted with 1 to 19 fluorine atoms, cyclic alkyl of 3 to 10 carbon atoms, (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. 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 easily suppressed 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. In addition, the compositions should still have a selectivity similar to that of the main herbicide in terms of crops. Of course, it is difficult to determine the respective combination in view of the myriad of available herbicides.

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

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.

Even before EP-0 282 303, herbicidal compositions comprising 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

The essence of the invention is to build new and herbicidal compositions

- 3 active mixtures or combinations containing said triazole derivative of the general 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 the germination and growth of undesirable vegetation in a selective manner with respect to crops such as rice, wheat and corn.

Surprisingly, it has been found that mixtures of said triazole derivatives with certain coherbicides selected from diphenyl ethers are particularly effective on a broad spectrum of weeds, while being selective in relation to crops and, moreover, have a synergistic effect.

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

ABOUT

wherein R is a linear alkyl group having 1 unsubstituted or substituted 1 branched alkyl group having 3 to unsubstituted or substituted by 1 to 10 carbon atoms, up to 19 fluorine atoms, carbon atoms, up to 19 fluorine atoms, a cyclic alkyl group having 3 to 10 carbon atoms, alkyl group having 1 up to 3 carbon atoms substituted by an alicyclic structure having 3 to 7 carbon atoms, phenyl or aralkyl having 7 to 9 carbon atoms; X ¹ is halogen or C 1 -C 3 alkyl; X ² is hydrogen, halogen or alkyl with az

Y ¹ is hydrogen or fluorine and Y ² is hydrogen or selected from the group of herbicides by fluorine atoms and at least one diphenyl ether type coherbicide.

It has been found that mixtures herbicidal activity in relation to herbicides, because they lack a weak invention have improved to intrinsic triazole activity against those weeds that are difficult to destroy by triazole derivatives alone

In addition, the spectrum of weeds on which the compositions of the invention are effective is broader compared to the triazole herbicide alone.

It should be noted that the selective properties to e.g. monocotyledonous crops such as cereals (including but not limited to wheat, maize and rice) have not suffered.

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 maintaining efficacy 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.

Preferred diphenyl ether herbicides are bifenox, acifluorfen, fluoroglycophene, fomesafen and oxyfluorfen.

The compositions of the invention may comprise a triazole derivative and a so-called triazole derivative. the coherbicide in any ratio, depending on the conditions of application and the type of herbicides used in the mixture.

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.

In another aspect, the present invention is also directed to the use of the above compositions for selectively controlling or inhibiting the growth or germination of unwanted plants by sequential or simultaneous application to plants, seeds or seeds or plants.

DETAILED DESCRIPTION OF THE INVENTION

It is evident that the individual components defined above in a mixture of m oz-be - APL also Ovan s to ~ ^_ with em en & R as tTifiy arebô'm'ieš'tä urč'éri xa seeds or plants 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 compositions comprising 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 herbicidal components, adjuvants or less common agricultural adjuvants. The application rates depend on the particular conditions of use and the particular herbicidal mixture.

Herbicidal compositions containing a triazole derivative and a co-herbicide, as well as formulations derived therefrom, including aqueous or anhydrous solution concentrates and aqueous suspensions that require dilution prior to use, are all exemplary embodiments of the present invention and are termed 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 compositions 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 such 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 sulfonic acid polyesters, diethylene glycol sulfonates in particular isooctylphenol 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, diamines such as ethylenediamine polyamines, alkoxylated amines and dispersants polyvinyl alcohol, lignin sulfonate alkyl naphthalenesulfonate, naphthalenesulfonate bis-naphthalenesulfonate.

are mixtures of ingredients, an inert solid filler, and dispersants. Inert 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) and piperazine aminotensides. methylcellulose, sodium, sodium polymers and polymethylene morpholine are preferred

Wettable powders containing a mixture of active one or more wetting agents solid fillers usually have insoluble active uniform mixtures and then a dispersant and 5 to 95 parts (preferably 5 to 50 parts) of an inert solid filler, all parts being parts by weight 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 which are aqueous suspensions or emulsions can be prepared by mixing an anhydrous solution of the mixture of the water components and the emulsifier with water until it is homogenized to form an emulsion of very 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. with kerosene, for 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 by weight of total solvent, based on oil.

The mixtures according to the invention which are the physically stable active ingredients, applied to the finely divided emulsifying particles, can also be mixtures of particles in the form of granules, containing the mixtures on the matrix of inert fillers or in the filler.

- 8 divided. 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 heat expanded vermiculite and finely divided 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 up to 5 parts by weight of surfactant per 100 parts by weight. clay particles (clay particles).

The compositions of the present invention may also contain falsified additives such as 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 Annual, 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 mixture is based on the relationship

Y (100-X)

E = X f ---------- 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 mixture A + B. In order to demonstrate synergism, the real effectiveness should be higher

as E. Example 1 Triazole compound according to the above general wherein X ¹ is chlorine, X ² is hydrogen, Y ¹ and Y ² are hydrogen -ČFsCF s is further j referred to as Compound A, suspension concentrate components. (SC) and containing about 42%

of formula (I), y and R are adjusted as mass. active

In this assay, Compound A was tested in combination with a diphenylether herbicide, called RH-0265 or fluoroglycophenethyl (Compete, trade name), a wettable squid. Three sets of treatment vessels were placed 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 MARDRIVE 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 of the BRSNV GERMO STEME LAMP plant were as follows

Matricaria chamomilla

Alopecur.u.s myosuroides

Oil seed rape, Oilseed rape

Geranium molie

Stellaria media

Lamium purpureum, Deadnettle species:

magenta

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 results obtained are summarized in Table 1 and show the average percentage of phytotoxicity from three replicates, evaluated 15 days after treatment.

T abuľka

LAMP £ o o c o - 'CM 2 p H <8 88 EXP and cu 2 2 p STEME H o o o <d xt OO _ O o O cn ir> f - ¹ 0 0 0 <«Λ P ~ <J \ EXP as? a GERMO “T * .....- Ss o o o <- 'd Ό O O O d m m y 0 0 0 <en xt · vn EXP 0- 00 t W d en vn BRSNX H Si o © o <- <—I ΓΊ 000 d S-t » H 5? © p © <en 30 p * EXP Cu, 00 Ό en tU d xt p- ALOMY Ï <000 OOO Ï <0-00 EXP i Ck X tu 0 0 O MATCH H U <000 0 p 0 xt 35 r> y 0 0 0 EXP cu S s s g Dose ai g / ha <n 0 <S 2 £ RH-0265 250 500 1000 A + RH-0265 62.5 + 250 62.5 + 500 62.5 + 1000

H

U ° <Tl

O O p v> c- c ~

Dose g / ha MATCH ALOMY BRSNX GERMO | STEME LAMP cu

X o \ t · ω - n

H o o <C ~ OO Os cu

X CM OO O U t V) O ~ o o v> in v>

OO Tt 00 CM

O oo oo θ 'Axis

O Ό O oo oo o \

OOQ v> v> Ό b S38

CM O MO '00

ACT WITH 70 about 00 WITH ABOUT 00 ABOUT 00 cu X 00 Ό cn tf 00 ch (U CM t Tt v> f * ACT about about about ABOUT ABOUT •ABOUT

CU x

W o o o o o

H

O o o o o o r oo oo oo oo oo oo

X © p O O p O

W 'f MO O- TJ- <2 O-

CD -C in" M0 CM ABOUT about within WITH § v> MO CM ABOUT about m s S VI o ra -X > from) '53 < CM + v> + + 1 The oi CM + + + 'WHAT + IN" v> IN" + about about IN" about about CM CM CM IN) CM IN) < - —- ¹ < CM CM

EXP in the table means the expected percentage of suppression, calculated according to the mathematical relationship above. ACT means true suppression as evaluated.

As shown in Table 1, no component of the mixture in itself provides acceptable suppression of selected plant species by the indicated doses (amounts). However, the composition can provide suppression of industrial importance (about 85%) at relatively low doses of each component.

The synergistic effect of the two herbicides used in combination is particularly evident on M. chamomilla, where herbicide A itself is weak. In oilseed rape, the synergistic effect is substantially visible at very low doses, whereas at higher doses no antagonistic effect could be measured. A very strong synergistic effect was seen on Stellaria media. In the case of Lamium purpureum, where A is fairly weak or poorly controlled, the A + RH-0265 mixture is well effective at low doses and the spectrum of action is thus broadened.

The synergistic phenomenon of the mixtures and the broader spectrum of action are unexpected. In addition, lower amounts of herbicides may be used to achieve the effect each component provides per se. Crop selectivity was good for all treatments.

Example 2

The same triazole compound as used in Example 1, hereinafter referred to as Compound A, was treated as a suspension concentrate (CS). In the test vessels in this greenhouse test, Compound A was tested in admixture with another diphenylether pesticide, bifenox as a technical material with 99% purity.

The plants were exposed to a photoperiod for 8 hours a day at 15 ° C; overnight (16 h) the temperature was 19 ° C. The plants were watered once a day with water.

The following plant species were treated in the glasshouse at the specified stage (immediately after germination).

BIDPI Bidens Pilosa L. 0.5 1

CASOB Cassia tora antc. 0,1 1

J. ABUTH

MATCH

herbicidal

Abutilon theophrasti medik. 0,1 1

Matricaria chamomilla 1.0 L combination was applied by spraying with volume

1000 l / ha.

Toxicity evaluation was performed by comparison with untreated control vessels on a scale of 0 to 5, where 0 means no visible effect and 5 means complete death. The results obtained from the evaluation after 15 days after treatment (DAT) are summarized in the table;

Table 2

Flupoxam bifenox BIDPI CASOB ABUTH MATCH g a.i./ha g a.i./Ha 0 0 0 0 0 0 31 0 4.5 4 3 0 62 0 4.9 3.75 3.5 2 125 0 5 3.75 3.5 3 31 2 5 2.5 3.5 0 62 2 5 3.5 4.75 2.5 125 2 5 4.25 4 2.5 31 8 5 3.75 4.9 1.5 62 8 5 4.5 4.9 4.75 125 8 5 4.25 5 4 31 31 4.9 3.75 5 3.5 62 31 5 4 4.9 5 125 31 5 4.5 5 5 0 2 0 0 1 0 0 8 1.5 1 4.75 2 0 31 3 3.5 5 4

Although at higher doses, the composition does not appear to provide greater than additive effects, at least to achieve the lethal doses of the herbicidal composition, most intermediate doses and even lower doses show synergistic effects on plant species tested after only 15 DATs. symptomatology already at low suppression by lower herbicidal each herbicidal component, amounts of bifenox (less than conventional a.i./ha) significantly increase the herbicidal compounds exemplified.

That is, early herbicidal doses and total concentrations as separate tables. The table also shows that small doses, i. 300-750 g triazole activity

Example

The effect of a mixture of the triazole compound of Example 1 with bifenox as in Example 2 was also assessed in a test vessel in a greenhouse for GALnP (Galli aparine). This test was essentially performed as in Example 2.

The herbicidal mixture was applied immediately after germination (at the growth stage, when the plant passes from the cotyledon to the sow leaf) and the evaluation of phytotoxicity was made 31 days after treatment (DAT) by comparison with untreated containers on a scale of 0 to 5 where 0 means no visible effect. and 5 means complete death of the plants.

Table 3

Bifenox g a. , i. / ha _t Flupoxam [g ai / ha] 0 4 8 16 32 0 0 0 2.5 3.5 3.8 31 3 3.8 4 4.9 4.9 62 3.5 4.5 4.5 4.9 4.9 125 4.5 4.5 4.9 4.9 4.9

It is clear from the above that almost complete suppression of GALAP can be achieved at low doses after 31 DATs as compared to single herbicidal components.

Claims (6)

PATENT CLAIMS A composition comprising a triazole compound of formula I wherein R is a straight chain alkyl of 1 to 10 carbon atoms, unsubstituted or substituted with 1 to 19 fluorine atoms, a branched alkyl group of 3 to 10 carbon atoms, unsubstituted or substituted with 1 to 19 fluorine atoms, cyclic (C 3 -C 10) alkyl, (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 the group of diphenyl ether type 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. A composition according to claim 1 or 2, characterized in that the diphenylether type herbicide is bifenox, acifluorfen, fluoroglycofen, fomesafen or oxyfluorfen. A herbicidal concentrate in the form of a solution, dispersion or emulsion comprising a 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 the composition according to claims 1 to 3 for selectively controlling or inhibiting the growth or germination of unwanted vegetation by subsequent or simultaneous application of a herbicidally effective amount of its components to plants, seeds or seed or plant planting sites. 'Lethylamine "