FR2778314A1 - Synergistic fungicidal composition for treating crops and grass - Google Patents

Abstract

A synergistic fungicidal composition contains: (1) a strobilurin analog (I); and (2) a fungicidal phosphorous acid derivative (II), especially fosetyl-Al, phosphorous acid itself, and its alkali or alkaline earth metal derivatives. The weight ratio of (I)/(II) is 0.004 - 1, preferably 0.0125 - 0.4. The strobilurin analogs are of formula (I): T = CH or N; R = H, halogen, 1-4C alkyl, or 1-4C haloalkyl; and n = 0 - 5. An Independent claim is also included for controlling fungi by applying the composition.

Description

Synergistic fungicidal composition comprising an analogous compound

strobilurin.

  The subject of the present invention is a synergistic fungicidal composition comprising a strobilurin-like compound and a process using said composition and intended to protect, curatively or preventively, the

  crops against fungal attacks.

  There are known, in particular from the German patent application DE 4423612 (WO 9601256), compounds analogous to the strobilurin with fungicidal action, making it possible to prevent the growth and development of fungi

  phytopathogens likely to attack crops.

  However, it is always desirable to improve the activity spectrum and the effectiveness of such fungicidal compounds, or to reinforce them by combining them with other molecules in order to obtain a more efficient product (association with a systemic fungicide , these fungicides being rather molecules of the "contact" type) or else to prevent the appearance of fungal strains resistant to these new fungicides. It is also very desirable to have fungicidal products benefiting from an improved persistence of action, such as to space over time.

  the number of phytosanitary treatments necessary for the proper control of pests.

  It is in any case particularly advantageous to be able to reduce the quantity of chemicals spread in the environment, while ensuring

  effective crop protection against fungal attacks.

  It has now been found that one (or more) of the foregoing objectives

  could be achieved by the fungicidal composition according to the present invention.

  The subject of the present invention is therefore firstly a synergistic fungicidal composition comprising at least one compound A of formula (I):

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  NN 1N-OMe C 0O (R) n I OMe (I) in which: Test CH or N, R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a group haloalkyl having 1 to 4 carbon atoms, these alkyl and haloalkyl groups being linear or branched and the substitution of the haloalkyl groups being complete or partial and n is a positive integer from 0 to 5 and at least one fungicidal compound B chosen from the group comprising phosphorous acid derivatives such as metallic phosphites such as

  fosetyl-Al, and phosphorous acid itself and its alkali or alkaline salts

  earthy. By alkyls of 1 to 4 carbon atoms, is meant the methyl, ethyl, n-propyl or isopropyl, n-butyl, tert-butyl or isobutyl groups J5. By haloalkyls of 1 to 4 carbon atoms, it is meant these abovementioned groups substituted by one or more identical or different halogen atoms if plurality (mixed halosubstitution). Finally, formula (I) allows

  to consider all isomeric forms.

  The fungicidal composition according to the invention advantageously comprises the components A and B in a weight ratio A / B, of between 0.004 and 1, of

preferably between 0.0125 and 0.4.

  It is understood that said fungicidal composition may contain a single compound B or more of such a compound, for example 1, 2 or 3 compounds B depending on the use for which it is intended. Likewise, the composition may comprise more than one compound A. The fungicidal composition according to the invention is preferred, for which the compound A is such that T is CH, R is Cl and n is 1, chlorine being preferably

in position 4.

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  Among the more especially preferred meanings of compound B defined above, more preferred is fosetyl AI. Unexpectedly, the composition according to the invention then significantly improves the action of the active ingredients taken separately for a number of fungi which are particularly harmful to crops, such as in particular the vine or solanaceae. This improvement is reflected in particular by a reduction in the doses of each of the constituents, which is particularly advantageous for the user and the environment. The fungicidal and / or bactericidal product (mixture) thus exhibits synergistic properties attested by the application of the method defined by Io Limpel, L.E., P.H. Schuldt and D. Lammont, 1962, Proc. NEWCC 16: 48-53, using the following formula, also known as Colby's formula:

E = X - Y - X.Y / 100

  in which: - E is the expected percentage of inhibition of the growth of the fungus by a mixture of the two fungicides A and B at defined doses, respectively equal to a and b - X is the percentage of inhibition observed by the fungicide and / or bactericide A at dose a, - Y is the percentage of inhibition observed by the fungicide and / or

bactericide B at dose b.

  When the percentage of inhibition observed of the mixture is greater than E, there is synergy. Preferably, when component B is fosetyl-Al, the A / B ratio is between 0.01 and 1, preferably between 0.033 and 0.4 for the whole

of the crops under consideration.

  In the particular case of turf, the A / B ratio will be between 0.004

  and 0.4, preferably between 0.0125 and 0.1.

  The structures corresponding to the common names of the fungicidal active ingredients appearing in the definition of B are indicated in at least one of the following 2 works:

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  - "The pesticide manual" edited by Clive TOMLIN and published by the British Crop Protection Council, 1 st edition, 1997; - the 1998 Phytosanitary Index, published by the Association of

  Agricultural Technical Coordination, 34th edition.

  Furthermore, works as general as the Chemical Abstracts are

  reference books fully accessible to those skilled in the art.

  The fungicidal composition according to the invention comprises, as active material, at least one compound A and at least one compound B in admixture with the

  solid or liquid supports, acceptable in agriculture and / or surfactants

  active also acceptable in agriculture. In particular, the usual inert supports and the usual surfactants can be used. These compositions cover not only the compositions ready to be applied to the culture to be treated by means of a suitable device, such as a spraying device, but also the concentrated commercial compositions which must be diluted before application to the culture. The term active ingredient denotes the combination of at least one compound A with at least one compound B. These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, agents thixotropes, penetration agents, stabilizers, sequestrants, etc. More generally, compounds A and B can be combined with all the solid or liquid additives corresponding to the usual techniques of

the formulation.

  In general, the compositions according to the invention usually contain from 0.05 to 95% (by weight) of active material, one or more solid or liquid supports and, optionally, one or more surfactants. By the term "support", in the present description, is meant an organic or mineral, natural or synthetic material, with which the active material is combined to facilitate its application to the aerial parts of the plant. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid

  (water, alcohols, in particular butanol etc ...).

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  The surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalene sulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines , substituted phenols (in particular alkylphenols or arylphenols), ester salts of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters of acids fatty acids and polyols, the derivatives containing sulfates, sulfonates and phosphates of the preceding compounds. The presence of at least one surfactant is generally essential when the active material and / or the inert support does not

  are not soluble in water and that the vector of the application is water.

  Thus, the compositions for agricultural use according to the invention can contain the active material within very wide limits, ranging from 0.05% to 95% (by weight). Their content of surfactant is advantageously between 5% and 40% by weight. Unless otherwise indicated the percentages given in this

  description, including claims, are by weight.

  These compositions according to the invention are themselves in forms

  quite diverse, solid or liquid.

  As forms of solid compositions, mention may be made of powders for

  dusting (active ingredient content of up to 100%) and granules.

  in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of active material in these granules being between 0.5 and 80% for the latter cases), the tablets or

effervescent tablets.

  The fungicidal composition according to the invention can also be used in the form of powders for dusting; one can also use a composition comprising 50 g of active material and 950 g of talc; one can also use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting. As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in

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  particularly water-soluble concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or spray powder),

pasta, gels.

  The concentrated suspensions, applicable in spraying, are prepared so as to obtain a stable fluid product which does not deposit 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 defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is sparingly or not very soluble: certain organic solids or mineral salts can be dissolved in the support to help

  prevent sedimentation or as antifreeze for water.

  1 As an example, here is a concentrated suspension composition:

Example SC 1:

  - active ingredient 500 g - polyethoxylated tristyrylphenol phosphate 50 g polvethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (defoamer) 1 g polysaccharide 1.5 g - water 316.5 g Wettable powders ( or powder to be sprayed) are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, from 0 to 30% of a wetting agent, from 3 to 20% of '' a dispersing agent, and, when necessary, from 0.1 to 10% of one or more stabilizers and / or other additives, such as

  penetration, adhesives, or anti-caking agents, dyes, etc ...

  To obtain sprayable powders or wettable powders, the active ingredients are intimately mixed in the appropriate mixers with the additional substances and ground with mills or other grinders

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  appropriate. This gives sprayable powders whose wettability and suspension are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very

  advantageously in particular for application to the leaves of plants.

  Instead of wettable powders, pasta can be made. The conditions and methods of making and using this pasta are similar

  to those of wettable powders or spraying powders.

  As an example, here are various compositions of wettable powders (or spraying powders):

Example PM I

  - active ingredient 50% - ethoxylated fatty alcohol (wetting agent) 2.5% ethoxylated phenylethylphenol (dispersing agent) 5% - chalk (inert support) 42.5%

Example PM 2:

  - active ingredient 10% - branched type oxo synthetic alcohol, in C13 ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75% neutral calcium lignosulfonate (dispersing agent) 12% - calcium carbonate (inert filler) qs 100%

Example PM 3:

  This wettable powder contains the same ingredients as in the previous example, in the following proportions - active material 75% - wetting agent 1.50% - dispersing agent 8% - calcium carbonate (inert filler) q.s.p. 100%

Example PM 4:

- active ingredient 90%

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  - ethoxylated fatty alcohol (wetting agent) 4% - ethoxylated phenylethylphenol (dispersing agent) 6%

Example PM 5

  - active material 50% - mixture of anionic and nonionic surfactants (wetting agent) 2.5% - sodium lignosulfonate (dispersing agent) 5% - kaolin clay (inert support) 42.5% Aqueous dispersions and emulsions, for example, the compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the

  present invention. The emulsions can be of the water-in-oil or oil- type.

  in water and they can have a thick consistency like that of a "mayonnaise". The fungicidal compositions according to the invention can be formulated in the form of water-dispersible granules also included in the scope

of the invention.

  These dispersible granules, of apparent density generally comprised between approximately 0.3 and 0.6 have a particle size generally comprised

  between about 150 and 2000 and preferably between 300 and 1500 microns.

  The active ingredient content of these granules is generally understood

  between about 1% and 90%, and preferably between 25% and 90%.

  The rest of the granule is essentially composed of a solid filler and optionally surfactant additives giving the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the selected filler is soluble or not in water. When the filler is water-soluble, it can be mineral or, preferably, organic. We have

  obtained excellent results with urea. In the case of an insoluble filler, this

  it is preferably mineral, such as for example kaolin or bentonite. It is then advantageously accompanied by surfactants (at a rate of 2 to 20% by weight of the granule) of which more than half is, for example, constituted by at least one dispersing agent, essentially anionic, such as a polynaphthalene

  alkaline or alkaline earth sulfonate or an alkaline or alkaline lignosulfonate

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  tcrreux, the rest being nonionic or anionic wetting agents such

  than an alkali or alkaline earth alkylnaphthalene sulfonate.

  Furthermore, although it is not essential, we can add

  other adjuvants such as defoamers.

  s The granule according to the invention can be prepared by mixing the necessary ingredients and then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). It generally ends with a crushing followed by sieving to the particle size chosen within the limits mentioned above. It is also possible to use granules obtained as

  previously and then impregnated with a composition containing the active material.

  Preferably, it is obtained by extrusion, operating as indicated

in the examples below.

  Example GD1: Dispersible granules In a mixer, 90% by weight of active material is mixed and

  % urea pearl. The mixture is then ground in a pin mill.

  A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roller extruder. A granule is obtained which is dried, then crushed and sieved, so as not to keep respectively

  than granules with a size between 150 and 2000 microns.

  Example GD2: Dispersible granules In a mixer, the following constituents are mixed: - active material 75% - wetting agent (sodium alkylnaphthalene sulfonate) 2% - dispersing agent (sodium polynaphthalene sulfonate) 8% - inert filler insoluble in water (kaolin) 15% This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between

0.15 and 0.80 mm.

  These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active ingredients, in particular fungicides,

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  the latter being in the form of wettable powders, or granules or

aqueous suspensions.

  With regard to the compositions suitable for storage and transport,

  they more advantageously contain from 0.5 to 95% (by weight) of active material.

  Another subject of the invention is a method of combating, for curative or preventive purposes, phytopathogenic fungi, for example crops or turf, characterized in that an effective and non-phytotoxic amount is applied to the aerial parts of the plants. of a combination of at least one compound A and at least one compound B, for example in a composition

fungicide according to the invention.

  The phytopathogenic fungi of cultures which can be combated by this process are in particular those: - of the group of oomycetes: - of the genus Phvtophthora such as Phytophthora infestans (late blight of solaneas, in particular of potato or tomato), Phytophthora citrophthora, Phytophthora capsici, Phytophthora cactorum, Phytophthora palmivora. Phytophthora cinnamoni, Phytophthora megasperma, Phytophthora parasitica, - of the Peronosporaceae family, in particular Plasmopara viticola (downy mildew), Plasmopara halstedei (sunflower downy mildew), Pseudoperonospora sp (especially downy mildew of cucurbits) lettuce), Peronospora tabacinae (downy mildew), - from the adelomycetes group: - from the genus Alternaria, for example Alternaria solani (alternaria of solaneas, and in particular from tomato and potatoes), - from the genus Guignardia, in particular Guignardia bidwellii (black rot of the vine), - from the group of Oidiums, for example powdery mildew of the vine (Uncinula necator); powdery mildew of vegetable crops, for example Erysiphe polygoni (cruciferous powdery mildew); Leveillula taurica, Erysiphe cichoracearum, Sphaerothecafuligena; (powdery mildew of cucurbits, compounds, tomatoes); Erysiphe communis (beet and cabbage powdery mildew); Erysiphe pisi (pea, alfalfa powdery mildew); Erysiphe polyphaga (bean and cucumber powdery mildew); Il 2778314 Erysiphe umbelliJèrarumn (powdery mildew of umbelliferae, especially carrot); Sphaerotheca humuli (hop powdery mildew); Erysiphe graminis (grain powdery mildew). - of the genus Septoria sp., - of the group of Basidiomycetes:

- of the genus Puccinia sp ..

  A classification made no longer by targeted mushrooms but by target cultures can be illustrated as below: - vine: powdery mildew (Uncinula necator), downy mildew (Plasmopara viticola), excoriosis (Phomopsis viticola) and black-rot (Guignardia bidwellii), - solaneas: downy mildew (Phytophthora infestans), alternaria (Alternaria solani) and rot (Botrytis cinerea), - vegetable crops: downy mildew (Peronospora sp., Bremia lactucae, Pseudoperonospora sp., alternariose (Alternaria sp.), sclerotiniosis (Sclerotinia sp.) , rot (Botrytis cinerea), powdery mildew (Erysiphe sp .; Sphaerothecafuliginea) -arboriculture: scab (Venturia inaequalis), powdery mildew (Podosphaera leucotricha) and moniliose (Moniliafructigena),-citrus: scab (Elsinois citrus fennel) and Phytophthora sp. diseases, -banane: Sigatoka (MAIycosphaerellafigiensis), -gazon: rust, powdery mildew, helminthosporiasis, telluric diseases

  (Microdochium nivale, Pythium sp., Rhizoctonia solani, ...).

  The fungicidal composition which is the subject of the invention is applied by means of different treatment methods such as: - spraying the aerial parts of the crops to be treated with a liquid comprising said composition, - dusting, incorporation of granules into the soil or powders,

  watering, injecting into trees or painting.

  Spraying a liquid on the aerial parts of crops to

  treating is the preferred treatment method.

  By "effective and non-phytotoxic amount" is meant an amount of composition according to the invention sufficient to allow the control or destruction of the fungi present or likely to appear on the cultures,

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  and causing for said cultures no significant symptom of phytotoxicity.

  Such an amount is likely to vary within wide limits depending on the fungus to be combated, the type of crop, the climatic conditions, and the compounds included in the fungicidal composition according to the invention. This quantity can be determined by systematic field trials, within the reach of

the skilled person.

  Furthermore, the application of the composition according to the invention can very

  well be done on genetically modified plants.

  The doses of use during the implementation of the process according to the invention will generally then be: on the vine, vegetable, solanea, banana, arboriculture, citrus crops: 1500 to 5000 g of compound B, for example. fosetyl-Al + 50 to 500 g / ha of compound A and more precisely 1000 to 3000 g + 100 to 400 g / ha, or a total dose of composition according to the invention of between 550 and 5500 g / ha,

  preferably between 1100 and 3400 g / ha.

  on grass: 5000 to 25000g of compound B, e.g. fosetyl-AI + 100 to 2000 g / ha of compound A and more precisely 10,000 to 20,000 g + 250 to 1,000 g / ha, or a total dose of composition according to the invention of between 5,100 and 27,000 g / ha,

  preferably between 10,250 and 21,000 g / ha.

  The following example is given purely by way of illustration of the invention,

that it does not limit in any way.

  Example: In vivo test of the association of compound A with fosetyl-Al on Plasmopara viticola (downy mildew of the vine) by preventive treatment 72 hours before contamination.

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  A suspension is prepared comprising compounds A and B in a liquid mixture consisting of a surfactant (oleate of polyoxyethylene derivative

sorbitan) and water.

  Compound A is such that T is CH, R is Cl and n is 1, the chlorine being in position 4. Component B is fosetyl-Al; the A / B ratio is 0.05, 0.07 and 0.1

(B / A = 20, 15 and 10).

  Vine cuttings (Vitis vinifera), Chardonnay variety, are grown in pots. When these plants are 2 months old (stage 8 to 10 leaves, height 10 to 15 cm), they are treated by spraying using the

suspension above.

  Plants used as controls are treated with a suspension

  similar but not containing active ingredient ("formulation blank").

  After 72 hours, each plant is contaminated by spraying with an aqueous suspension of Plasmopara viticola spores obtained from sporulated leaves contaminated 7 days previously. These spores are suspended at the rate of 100,000 units per cm3 of inoculum. Contamination is carried out by

  spraying the inoculum on the lower surface of the leaves.

  Contaminated plants are then incubated for seven days at

  -22 'C at 90-100% relative humidity under natural light.

  The reading is done 7 days after the contamination, in comparison with the control plants which makes it possible to define the percentage of efficiency according to the following formula:% practical efficiency = 100 x (% control contamination -% test contamination) /% control contamination The theoretical efficiency according to Colby's formula is calculated according to the following formula:

  % theoretical efficiency A + B =% eff. practical A +% eff. practice B - (% eff.

  practical A x% eff. practice B / 1 00)

III. Results.

Practical efficiency:

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  A / fosetyl-AlOppm 2 4 8 16 31 6! 125 Oppm O O O 0 0 0 O 3.7 11.1

0.4 3.7 7.4 11.1 11.1

0.8 7.4 18.5 25.9 25.9

1.6 44.4 63 75.9 63

3.1 75.9 87 96.3 97.4

  6.2 d 90.7 1.9 100 99.3 12.5 100 l 100 100 Theoretical efficiency (Colby) Afosetyl-Al 0 Oppm2 4 8 16 31 62 125 0 ppm 0 O o O 0 O 0 3.7 11 , 1

0.4 3.7 [3.70 3.70 3.70

0.8 7.4 7.40 d 7.407.40

1.6 44.4 44.40 44.4044.40

3.1 75.9 75.9075.90 j76, l79

6.2 90.7 90.7091.04 91.73

12.5 100 100.00 100.00

  Synergy: A / fosetyl-A1O ppm 2 4 8 16 31 62 125 0 ppm

0.4 4 7 7

0.8 1 19 19

1.6 [j J 19 32 19 ji__ l5 2778314

3.1 1 20 1 21

6.2 1 20 9 0

12.5 I___ _21 8

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Claims (12)

  1. Synergistic fungicidal composition comprising at least one compound A of formula (I): NN N-OMe C = 0 (R) n OMe (I) in which T is CH or N. R is a hydrogen atom, an atom of halogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, these alkyl and haloalkyl groups being linear or branched and the substitution of the haloalkyl groups being complete or partial and n is an integer positive from 0 to 5; and at least one fungicidal compound B chosen from the group comprising phosphorous acid derivatives such as metallic phosphites such as   fosetyl-Al. and phosphorous acid itself and its alkali or alkaline salts   earthy; said composition comprising components A and B in an A / B weight ratio of between 0.004 and 1, preferably between 0.0125 and 0.4, 2. fungicidal composition according to claim 1 characterized in that the   compound A is the compound of formula (I) is such that T is CH, R is CI and n is 1.   3. fungicidal composition according to one of claims I to 2, characterized in   that compound B is fosetyl Al.   4. fungicidal composition according to any one of claims 1 to 3,   characterized in that the A / B ratio is between 0.01 and 1, preferably between 0.033 and 0.4. 17 2778314   5. fungicidal composition according to any one of claims I to 3,   characterized in that in the case of turf the A / B ratio is between 0.004   and 0.4, preferably between 0.0125 and 0.1.   6. fungicidal composition according to any one of claims 1 to 5,   characterized in that it comprises compounds A and B in admixture with   solid or liquid supports acceptable in agriculture and / or surfactants   active also acceptable in agriculture.   7. fungicidal composition according to any one of claims 1 to 6,   characterized in that it comprises from 0.05 to 95% (by weight) of active material.   8. Method for controlling phytopathogenic fungi in a medium, characterized in that at least one compound A and at least one compound B are applied to said medium, these compounds being as defined in claim 1, and the combination of these compounds being in a total effective and non-phytotoxic amount 9. A method of combating, as a curative or preventive measure, against phytopathogenic fungi of crops or turf, characterized in that an effective and non-phytotoxic amount of a   A fungicidal composition according to any of claims 1 to 7.   10. Method for combating phytopathogenic fungi in cultures according to claim 9, characterized in that a dose of between 550 and   5500 g / ha, preferably between 1100 and 3400 g / ha, of composition.   11. A method of controlling phytopathogenic fungi in turf according to claim 9, characterized in that a dose of between 5100 is applied.   and 27,000 g / ha, preferably between 10,250 and 21,000 g / ha, of composition.   12. A product comprising at least one compound A as defined in claim 1 and at least one compound B as defined in claim I for the control of phytopathogenic fungi in a medium by application simultaneous.