GB2308301A - Synergistic fungicidal mixture of triticonazole with cyprodinil and/or fludioxonil for the protection of crop propagation products and crops therefrom - Google Patents

Abstract

A method for the preventive or curative protection of crop propagation products (and of the crops resulting therefrom) against fungal diseases comprises treating the products with triticonazole [which is 2-(4-chlorobenzylidene)-5,5-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-1 -cyclopentanol] and a compound (I) chosen from cyprodinil [which is 2-phenylamino-2-cyclopropyl-6-methylpyrimidine] and fludioxonil [which is 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile], the compound (I) having activity against leaf stripe and against fusaritoxicosis, either simultaneously, separately or sequentially. A combined product comprising triticonazole and a compound (I), optionally with agriculturally acceptable inert support and surfactant is also disclosed.

Description

NEW FUNGICIDAL COMPOSITIONS The present invention relate. to fungicidal compositions for use in particular in protecting plant seeds. The invention also relates to a method for protecting plant propagation products, e.g. seeds, and the plants resulting therefrom from fungal diseases.

Triticonazole is known, in particular from patent application EP 378,iS3, for its fungicidal efficacy.

However, the efficacy of this compound is not entirely satisfactory, in particular as regards barley leaf stripe (due to Pyrenophora graminee).

It is, moreover, always desirable to reduce the doses of chemical products spread into the environment to control fungal attack on crops, in particular by reducing the product application doses, and to widen the possibilities of choice offered to the grower so that he find the solution which is best suited to his specific problem One aim of the invention is thus to provide a novel fungicidal composition which is useful for the problems outlined above.

Another aim of the invention is to propose a novel fungicidal composition which is useful in the preventive and curative treatment of cereal disease., in particular barley and wheat diseases.

It has now been found that these aims can partly or totally achieved by means of the fungicidal compositions according to the present invention.

The synergistic fungicidal compositions according to the invention are characterized in that they comprise triticonazole and a compound (I) with activity against leaf stripe and against fusaritoxicosis, chosen from cyprodinil and fludioxonil.

The triticonazole/compound (I) ratio is defined as being the ratio of the weight of these compounds. This is likewise the case for any ratio of chemical compounds which is mentioned later in the present text, insofar as a definition different to this ratio is not expressly indicated.

Triticonazole is 2- (4-chlorobenzylidene) .5,5- dimethyl-l- (lH-l,2,4-triazol-l-ylmethyl) -1- cyclopentanol, which is described in particular in patent application EP 378,953 mentioned above.

Cyprodinil, also known as 2-phenylamino-4-cyclopropyl 6-methylpyrimidine, is described in patent application EP 310,550. Fludioxonil is 4-(2,2-difluoro-l,3- benzodioxol-4-yl)pyrrole-3-carbonitrile and is described in the Pesticide Manual, 10th edition (1994), by Clive Tomlin, published by the British Crop Protection Council and the Royal Society of Chemistry, page 482.

The compositions according to the invention are most particularly useful for treating the seeds of cereals (barley and wheat in particular). They are also useful for treating potato, cotton seeds, pea seeds, rapeseed seeds, corn seeds, flax seeds, grass seeds or the seeds of forest trees (in particular resiniferous trees).

These compositions appreciably improve the respective and isolated action of triticonazole and of compound I for certain fungi which are particularly harmful to crops, in particular to barley, while at the same time retaining an absence of phytotoxicity towards these crops. This therefore leads to an improvement in the spectrum of activity and a possibility of decreasing the respective dose of each active material used, the latter quality being particularly advantageous for readily appreciable ecological reasons.

The term synergistic effect is understood to have the meaning defined by Colby S.R. in an atticle entitled "Calcul des rponsee synergiques et antagonistes des combinaisons herbicides" (Calculation of the synergistic and antagonist responses of herbicidal combinations] published in the review Weeds, 1967, 15, p. 20-22. This article uses the formula: E = X + Y - XY/100 in which E represents the expected percentage inhibition of the disease for the combination of the two fungicides at defined doses (for example equal to x and y respectively), X is the observed percentage of inhibition of the disease by triticonazole at a defined dose (equal to x), Y is the observed percentage of inhibition of the disease by the compound (I) at a defined dose (equal to y).When the observed percentage of inhibition of the combination is greater than E, there is a synergistic effect.

The triticonazole/compound (I) ratio is chosen so as to produce a synergistic effect.In general, they the triticonazole/compound (I) ratio in the compositions according to the invention is between 0.05 and 20, preferably between 0.1 and 10, even more preferably between 0.2 and 8.

The triticonazole/compound (I) ratio ranges indicated above do not in any way imply a limitation of the scope of the invention, but rather are given as a guide, a person skilled in the art being entirely able to carry out complementary tests to find other values of the ratio of doses of these two compounds for which a synergistic effect is observed.

Besides triticonazole and the compound (I), the composition according to the invention comprise an agriculturally acceptable inert support and optionally an agriculturally acceptable surfactant. In the following text, the term active material is understood to denote the combination of triticonazole with the compound (I).

In the present account, the term "support" is understood to denote a natural or synthetic organic or inorganic material with which the active material is combined to facilitate its application to the plant, on seeds or on the soil. This support is thus generally inert and it must be agriculturally acceptable, in particular on the seed treated. The support may be solid (in particular: clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers) or liquid (in particular: water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases).

The surfactant may be an emulsifying, dispersing or wetting agent of ionic or nonionic type.

Mention may be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsuiphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty gamines, substituted phenols (in particular alkyiphenols or aryiphenols), salts of suiphosuccinic acid esters, taurine derivatives (in particular alkyltaurates), and phosphoric esters of polyoxyethylated alcohols or phenols. The presence of at least one surfactant is often required since the active material and/or the inert support are not watersoluble and since the vector agent for the application is water.

These compositions may also contain other ingredients of any kind such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, pigments, dyes and polymers.

More generally, the compositions according to the invention may be combined with any solid or liquid additive associated with the usual formulation techniques for application of the seed treatment in particular.

In this respect, it will be noted that in the jargon used by those skilled in the art, the term seed treatment in fact refers to the treatment of grains.

The application techniques are well known to those skilled in the art and may be used within the context of the present invention.

Mention may be made, for example, of the application of films or coatings.

Among the compositions which may generally be mentioned are solid or liquid compositions.

Solid composition forms which may be mentioned are powders for sprinkling or dispersion (with an active material content which may range up to 100 %) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support or by granulation starting with a powder (the active material content in these granules generally being between 1 and 80 % for the latter cases). In this specification, including the accompanying claims, percentages are by weight unless otherwise specified.

The compositions may also be used in the form of a powder for sprinkling; it is thus possible to use a composition comprising 50 g of active material, 10 g of finely divided silica, 10 g of organic pigment and 970 g of talc; these constituents are mixed together and ground and the mixture is applied by sprinkling.

As liquid composition forms or forms intended to make up liquid compositions during application, mention may be made of solutions, water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or powders to be sprayed), pastes and dispersible granules.

The emulsifiable or soluble concentrates usually comprise 10 to 80 % active material whereas the ready-to-use emulsions or solutions contain 0.01 to 20 % active material.

For example, in addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20 % of suitable additives such as the stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes or adhesives mentioned above.

Starting with these concentrates, emulsions of any desired concentration, which are particularly suitable for application to seeds, may be obtained by dilution with water.

The concentrated suspensions, which can also be applied by spraying, are prepared so as to obtain a stable fluid product which does not settle out, and they usually contain from 10 to 75 % of active material, from 0.5 to 15 % of surfactants, from 0.1 to 10 % of thixotropic agents, from 0 to 10 % of suitable additives such as pigments, dyes, anti-foaming agents, corrosion inhibitors, stabilizers, penetration agents and adhesives and, as support, water or an organic liquid in which the active material is insoluble or sparingly soluble: certain solid organic materials or mineral salts may be dissolved in the composition to help to prevent sedimentation or to act as antifreezes for the water.

The wettable powders (or powders to be sprayed) are usually prepared such that they contain 20 to 95 % of active material, and they usually contain, in addition to the solid support, from 0 to 5 % of a wetting agent, from 3 to 10 % of a dispersing agent and, when necessary, from 0 to 10 % of one or more stabilizers and/or other additives such as pigments, dyes, penetration agents, adhesives, anti-caking agents, etc.

In order to obtain these powders to be sprayed or wettable powders, the active materials are intimately mixed with the additional substances in suitable mixers and the mixture is ground with mills or other suitable grinders. Powders to be sprayed whose wettability and placing in suspension are advantageous are thereby obtained; they may be placed in suspension with water at any desired concentration and these suspensions can be used very advantageously in particular for application to seeds.

In place of wettable powders, pastes may be produced. The conditions and modes of production and use of these pastes are similar to those for the wettable powders or powders to be sprayed.

The dispersible granules are usually prepared by agglomeration, in suitable granulating systems, of compositions of wettable powder type.

As has already been stated, the aqueous dispersions and emulsions, for example the compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are included within the general scope of the present invention. The emulsions may be of the water-in-oil or oil-in-water type and they may have a thick consistency such as that of a flmayonnaisefl.

The fungicidal compositions according to the invention usually contain from 0.5 to 95 % of the triticonazole and compound (I) combination.

This may be the concentrated composition, that is to say the commercial product containing triticonazole and compound I. It may also be the dilute composition ready to be applied to the seeds to be treated. In the latter case, the dilution with water may be carried out either using a commercial concentrated composition containing triticonazole and compound I (this mixture is referred to as the "readyto-use" mixture or the "ready mix"), or by mixing at the time of use (referred to as the "tank mix") two commercial, preferably concentrated, compositions each containing triticonazole or compound (I).

The invention also relates to a method of preventive or curative protection of crop multiplication products, as well as of the crops resulting therefrom, against fungal diseases, characterized in that the said products are treated, e.g. covered, with an effective and non-phytotoxic dose of a composition according to the invention.

Among the crop multiplication products concerned, mention may be made in particular of seeds or grains, and tubers.

It is preferred to use the method according to the invention in the case of seeds.

As has been mentioned before, the modes of covering the crop multiplication products, in particular seeds, are well known in the art and make use in particular of film or coating techniques.

Among the crops and diseases, including those of seeds or grains, towards which the method according to the invention is directed, mention may be made of: - wheat, as regards controlling the following diseases: fusaritoxicoses (Microdochium nivale and Fusarium roseum), rot (Tilletia caries, Telletia controversa or Tilietia indica), leaf spot (Septoria nodorum); - wheat, as regards controlling the following diseases of the aerial parts of the plant: eyespot (Pseudocercosporella herpotrichoides), mildew (Erysiphe grains forms specie tritici), rusts (Puccinia striiformis and Puccinia recondita) and leaf spots (Septoria tritici and Septoria nodorum); - barley, as regards controlling the following diseases of seeds: leaf stripe (Pyrenophora gramfnea, Pyrenophora teres and Cochliobolus sativue), loose smut (Ustilago nuda) and fusaritoxicoses (Microdochium nivale and Fusarium roseum), - barley, as regards controlling the following diseases of the aerial parts of the plant: eyespot (Pseudocercosporella herpotrichoides), leaf stripe (Pyrenophora teres and Cochliobolus sativus), mildew (Frygiphe gruinis forma specie hordei), dwarf rust (Puccini a hordei) and leaf blotch (Rhynchosporium secalis); - potato, as regards controlling tuber diseases (in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani); - cotton, as regards controlling the following diseases of young plants obtained from seeds:: damping-off and necrosis of the root collar (Rhizoctonia solani , Fusarium oxysporum), black rot of the roots (Thielaviopsis basicola); - pea, as regards controlling the following seed diseases: anthracnose (Ascochyte piss, Mycosphaerella pinodes), fusaritoxicosis (Fusariun: oxysporum), grey rot (Botrytis cinerea), - rapeseed, as regards controlling the following diseases of the seeds:Phoma lingan: and Al ternaria brassicaet - corn, as regards controlling the seed diseases: (Rhizopus sp., Penicilliuni sp., Trichoderma sp., Aspergillus sp. and Gibberella fujikuroi); - flax, as regards controlling the seed disease: Alternaria linicola; - grasses, as regards controlling Hen:inthosporium sp., Fusarium sp.; - forest trees, as regards controlling damping-off (Fusarium oxysporum, Rhizoctonia solani).

Wheat and barley are the preferred crops for use of the method according to the invention.

The expression "effective and non-phytotoxic dose" is understood to refer to an amount of composition according to the invention which is sufficient to allow the control or destruction of the fungi present or liable to appear on the crop multiplication products, in particular seeds, and not entailing any substantial symptoms of phytotoxicity for the said seeds or for the crops resulting from the growth of these seeds. Such an amount may vary within a wide range, in particular depending on the fungus to be controlled, the type of crop and the climatic conditions. This amount may be determined by systematic field trials, which are within the capability of a person skilled in the art.

The dose of composition applied is generally advantageously such that the dose of triticonazole is between 1 and 400 g/100 kg of seeds, preferably between 2 and 200 g/100 kg, and that the dose of compound (I) is between 2 and 400 g/100 kg of seeds, preferably between 3 and 200 g/100 kg.

When, according to a preferred variant of the invention, it is sought to protect wheat and barley against fungal diseases, the dose of composition applied is advantageously such that the dose of triticonazole is between 2 and 150 g/100 kg of seeds, preferably between 3 and 120 g/100 kg, and that the dose of compound (I) is between 2 and 50 g/100 kg of seeds, preferably between 3 and 20 g/100 kg.

The examples which follow are given, without any limitation being implied, to show the advantageous properties of the compositions according to the invention and demonstrate a synergistic effect according to the Colby definition.

Example 1: in vivo greenhouse test of a composition comprising a mixture of triticonazole and cyprodinil on Mçerodoehçum nivale which is responsible for fusaritoxicosis in wheat: A triticonazole formulation, which is a concentrated aqueous suspension containing 211 g/l of triticonazole, and a commercial cyprodinil formulation, which is a dispersible granulate containing 75 % cyprodinil, are used.

The following are prepared by simple dilution with water: - an aqueous suspension containing triticonazole; - aqueous suspensions containing cyprodinil; and - aqueous suspensions containing a mixture of these 2 compounds in the ratio: triticonazole/ cyprodinil equals 0.25; 0.5; 1; 2; 4; 8.

Grains of durum wheat (Ixos variety) naturally contaminated (40 %) with Microdochiun: nivale are treated by spraying with the suspensions prepared above, at a rate of 1.5 1 of suspension per 100 kg of seeds. The doses of active materials, expressed in g/100 kg, are indicated in the table below.

These grains are sown (25 grains per pot) into pots filled with compost/pozzolana which are placed in a greenhouse at a temperature of SOC and a relative humidity of 70 % for a period of 3 weeks.

These pots are then placed at 100C for a period of 1 week.

The results are then read. For this, the number of healthy plants per pot are counted. A healthy plant is a plant which has developed normally, as opposed to a sick plant whose leaves are deformed and atrophied.

The number of sick or destroyed plants, which is equivalent to A, is then determined by subtracting the number determined above from the total number of grains sown.

The number of sick plants in the case of the control test (contaminated and untreated grains), which is equivalent to B, is then determined.

The efficacy E (expressed as %) of the fungicidal treatment is then calculated using the formula: E r (B - A) x 100/B The fungicidal efficacy results corresponding to the treatment doses indicated (expressed in g/100 kg of seeds) are collated in the table below:

cyprodinil 0 0.62 1.25 2.5 5 10 20 (doses in g/ 100 kg of seeds) tri ticonazole ~ 7 13 37.4 52.2 52.2 68.7 5 13 22.6 37.4 51.3 60 80 80.9 Example 2: in vivo greenhouse test of a composition comprising a mixture of triticonazole and cyprodinil on Pyrenophora graminea which is responsible for leaf stripe in barley: A triticonazole formulation, which is a concentrated aqueous suspension containing 211 g/l of triticonazole, and a commercial cyprodinil formulation, which is a dispersible granulate containing 75 % cyprodinil, are used.

The following are prepared by simple dilution with water: - an aqueous suspension containing triticonazole; - aqueous suspensions containing cyprodinil; and - aqueous suspensions containing a mixture of these 2 compounds in the ratio: triticonazole/ cyprodinil equal to 2 and 4.

Grains of barley (Agneta variety) naturally contaminated (30 %) with Pyrenophora gamines are treated by spraying with the suspensions prepared above, at a rate of 1.5 1 of suspension per 100 kg of seeds. The doses of active materials, expressed in g/100 kg, are indicated in the table below.

These grains are sown (25 grains per pot) into pots filled with compost/pozzolana which are placed in a greenhouse at a temperature of 50C and a relative humidity of 70 % for a period of 3 weeks.

These pots are then placed at 10 C for a period of 1 week, then at 200C for a period of 3 weeks.

The results are then read.

The number of sick plants, which can be recognized by the presence of whitish stria arranged parallel to the central nervure of the leaves, which is equivalent to A, is determined.

The number of sick plants in the case of the control test (contaminated and untreated grains), which is equivalent to B, is likewise determined.

The efficacy E (expressed as %) of the fungicidal treatment is then calculated using the formula: E = (B - A) x 100/B The fungicidal efficacy results corresponding to the treatment doses indicated (expressed as g/100 kg of seeds) are collated in the table below:

cyprodinil 0 1.25 2.5 (doses in g/100 kg of seeds) tri ticonazole 0 - 39.7 80.6 5 58.5 93.1 100 Example 3: in vivo greenhouse test of a composition comprising a mixture of triticonazole and fludioxonil on Pyrenophora guinea which is responsible for leaf stripe in barley: Example 2 is repeated, using a commercial formulation of fludioxonil, which is a concentrated suspension containing 25 g/l of fludioxonil, and a concentrated ready-to-use suspension comprising 25 g/l of triticonazole and 25 g/l of fludioxonil. The following are prepared by simple dilution with water: - aqueous suspensions containing triticonazole; - aqueous suspensions containing fludioxonil; and - aqueous suspensions containing a mixture of these 2 compounds in the ratio: triticonazole/ fludioxonil equal to 1.

The fungicidal efficacy results corresponding to the treatment doses indicated (expressed in g/100 kg of seeds) are collated in the table below:

fludioxonil 0 0.3 0.6 (doses in g/100 kg of seeds) triticonazole 0 - 44.8 72.4 0.3 46.6 92.2 - 0.6 73.5 . 100 According to a further feature of the present invention there is provided a combined product comprising triticonazole, which is 2-(4 chlorobenzylidene) -5,5-dimethyl-1- (lH-112,4-triazol-1- ylmethyl)-l-cyclopentanol, and a compound (I) with activity against leaf stripe and against fusaritoxicosis, chosen from cyprodinil, which is 2phenylamino-4 - cyclopropyl - 6 -methylpyrimidine and fludioxonil, which is 4- (2,2-difluoro-l, 3-benzodioxol- 4-yl)pyrrole-3-carbonitrile for simultaneous, separate or sequential application in the control of fungal disease of plant multiplication products.

Claims (16)

CLAY

1. Synergistic fungicidal compositions, characterized in that they comprise triticonazole, which is 2- (4-chlorobenzylidene) -5, S-dimethyl-l- (lH- 1, 2,4-triazol-l-ylmethyl) -1-cyclopentanol, and a compound (I) with activity against leaf stripe and against fusaritoxicosis, chosen from cyprodinil, which is 2-phenylA-;no-4-cyclopropyl-6-methylpyrimidine and fludioxonil, which is 4- (2, 2-difluoro-l, 3-benzodioxol- 4-yl)pyrrole-3-carbonitrile,

2. Fungieidal compositions according to Claim 1, characterized in that the triticonazole/ compound (I) weight ratio is between 0.05 and 20, preferably between 0.1 and 10, even more preferably between 0.2 and 8.

3. Fungicidal compositions according to either of Claims 1 and 2, characterized in that they also comprise an agriculturally acceptable inert support and optionally an agriculturally acceptable surfactant.

4. Fungicidal compositions according to any one of Claims 1 to 3, characterized in that they contain from 0.5 to 95 % by weight of the triticonazole and compound (I) combination.

5. Method for the preventive or curative protection of crop multiplication products, and of the crops resulting therefrom against fungal diseases, characterised in that the products are treated with triticonazole, which is 2- (4-chlorobenzylidene) -5,5- dimethyl-l-(lH-1,2,4-triazol-1-ylmethyl)-1- cyclopentanol, and a compound (I) with activity against leaf stripe and against fusaritoxicosis, chosen from cyprodinil which is 2-ph.nylamino-4-cyclopropyl-6- methylpyrimidine and fludioxonil, which ie 4-(2,2 difluoro-1, 3-benzodioxol-4-yl)pyrrole-3-carbonitrile.

6. Method for the preventive or curative protection of crop multiplication products, and of the crops resulting therefrom, against fungal diseases, characterized in that the said products are treated with an effective and non-phytotoxic dose of a composition according to any one of Claims 1 to 4.

7. Method according to Claim 5, characterized in that the crop multiplication products are seeds or tubers.

8. Method according to either of Claims 5 and 6, characterized in that the crop multiplication products are seeds.

9. Method according to any one of Claims 5 to 7, characterized in that the crops are wheat, barley, potato, cotton, pea, rapeseed, corn, flax, grasses or forest trees.

10. Method according to any one of Claims 5 to 8, characterized in that the crops are wheat or barley.

11. Method according to any one of Claims 5 to 9, characterized in that the dose of triticonazole per 100 kg of seeds is between 1 and 400 g/100 kg, preferably between 2 and 200g/lOOkg, and the dose of compound (I) per 100 kg of seeds is between 2 and 400g/lOOkg, preferably between 3 and 200g/lOOkg.

12. Method according to Claim 9, characterized in that the dose of triticonazole per 100 kg of seeds is between 2 and 150g/lookg, preferably between 3 and 120g/100kg, and that the dose of compound (I) per 100 kg of seeds is between 2 and 50g/lOOkg, preferably between 3 and 20g/l0okg.

13. A combined product comprising triticonazole, which is 2-(4-chlorobenzylidene)-5,5 dimethyl-l-(lH-1,2,4-triazol-1-ylmethyl)-l- cyclopentanol, and a compound (I) with activity against leaf stripe and against fusaritoxicosis, chosen from cyprodinil, which is 2-phenylamino-4cyclopropyl-6-methylpyrimidine and fludioxonil, which is 4-(2,2-difluoro-1,3-benzodioxol-4yl)pyrrole-3-carbonitrile for simultaneous, separate or sequential application in the control of fungal disease of plant multiplication products.

14. A fungicidal composition according to claim 1, substantially as hereinbefore described.

15. A method according to claim 5, substantially as hereinbefore described.

16. A product according to claim 13, substantially as hereinbefore defined.