ZA200105989B

ZA200105989B - Synergic fungicide composition comprising a compound analogue of strobilurin.

Info

Publication number: ZA200105989B
Application number: ZA200105989A
Authority: ZA
Inventors: Patrice Duvert
Original assignee: Aventis Cropscience Sa
Priority date: 1998-12-22
Filing date: 2001-07-20
Publication date: 2002-07-22
Also published as: JP2002532521A; CN1335748A; WO2000036916A1; PL355562A1; BR9917114A; KR20010104318A; EP1139748A1; MXPA01006508A; AU1866400A; FR2787295A1; HK1041787A1; CA2356818A1

Description

A

Synergistic fungicidal composition comprising a compound analogous to strobilurin.

The subject of the present invention is a synergistic fungicidal composition comprising a compound analogous to strobilurin and a process which makes use of the said composition and which is intended for the curative or preventive protection of crops against fungal attacks.

Compounds analogous to strobilurin with a fungicidal effect are known, in particular from

European Patent Application EP 460 575, which make it possible to prevent the growth and the development of phytopathogenic fungi capable of attacking crops.

However, it is always desirable to improve the spectrum of activity and the effectiveness of such compounds with a fungicidal effect or to reinforce them by combining them with other molecules in order to obtain a more effective product (combination with a systemic fungicide, these fungicides instead being molecules of "contact" type) or alternatively to prevent the appearance of fungal strains which are resistant to these new fungicides.

It is also highly desirable to have available fungicidal products which enjoy an improved persistance of effect, likely to space out in time the number of plant-protection treatments necessary for satisfactory control of the parasites.

It is, in any event, particularly

A J

A} advantageous to be able to decrease the amount of chemicals distributed in the environment, while ensuring high-performance protection of crops against fungal attacks.

It has now been found that one (or a number) of the above objectives could be achieved by virtue of the fungicidal composition according to the present invention.

The subject of the present invention is therefore, in first place, a synergistic fungicidal composition comprising at least one compound A of formula (Ia) or (Ib):

Meo CF,

MeO_ ~ : “N”~ TCOOMe (1a)

Me OCF,

MeO, _ ~ “N” TCOOMe (Ib) and at least one fungicidal compound B chosen from the group comprising derivatives of phosphorous acid, for example metal phosphites, such as fosetyl-Al, and phosphorous acid itself and its alkali metal or

~

N alkaline-earth metal salts.

The fungicidal composition according to the invention advantageously comprises the components A and

B in an A/B ratio by weight of between 0.004 and 1, preferably between 0.0075 and 0.2.

It is clearly understood that the said fungicidal composition can contain a single compound B or more than one such compound, for example 1, 2 or 3 compounds B, according to the use for which the composition is intended. Similarly, the composition can comprise more than one compound A, even if the compound of formula (Ia) (trifloxystrobin) is preferred in the present invention.

Preference is further given, among the more especially preferred meanings of the compound B defined above, to fosetyl Al. In an entirely unexpected way, the composition according to the invention then significantly improves the effect of the active materials taken separately with respect to a number of fungi which are particularly harmful to crops, for example in particular grapes or the Solanaceae. This improvement is reflected in particular by a decrease in the doses of each of the constituents, which is particularly advantageous for the user and the environment. The fungicidal product thus exhibits synergistic properties attested by application of the method defined by L.E. Limpel, P.H. Schuldt and

D. Lammont, 1962, Proc. NEWCC 16, 48-53, using the

~ following formula, also known as the Colby 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 with the fungicide and/or bactericide A at the dose a, - Y is the percentage of inhibition observed with the fungicide and/or bactericide B at the dose b.

There is synergy when the percentage of inhibition observed for the mixture is greater than E.

Preferably, when the component B is fosetyl-Al, the A/B ratio is between 0.005 and 1, preferably between 0.017 and 0.2, for all the crops envisaged. In the specific case of lawns, the A/B ratio will be between 0.004 and 0.1, preferably between 0.0075 and 0.05.

The structures corresponding to the common names of the fungicidal active materials which appear in the definition of B are shown in at least one of the following 2 works: - "The Pesticide Manual", edited by Clive

Tomlin and published by The British Crop Protection

Council, 11th edition, 1997; - 1'Index phytosanitaire [Plant-protection index] 1998, published by l'Association de Coordination

Technique Agricole [Agricultural Technical Coordination

Association], 34th edition.

The fungicidal composition according to the invention comprises, as active material, at least one 5 compound A and at least one compound B as a mixture with solid or liquid vehicles which are acceptable in agriculture and/or surface-active agents which are also acceptable in agriculture. In particular, the inert and conventional vehicles and the conventional surface- active agents can be used. These compositions cover not only compositions which are ready to be applied to the crop to be treated by means of a suitable device, such as a spray device, but also commercial concentrated compositions which have to be diluted before application to the crop. The combination of at least one compound A with at least one compound B is denoted as active material.

These compositions can also contain any kind of other ingredients such as, for example, protective colloids, adhesives, thickening agents, thixotropic agents, penetrating agents, stabilizing agents, sequestering agents and the like. More generally, the compounds A and B can be combined with all the solid or liquid additives corresponding to the conventional formulating techniques.

Generally, the compositions according to the invention usually contain from 0.05 to 95% (by weight) of active material, one or more solid or liquid vehicles and, optionally, one or more surface-active agents.

In the present account, the term "vehicle" denotes a natural or synthetic, organic or inorganic material with which the active material is combined to facilitate its application on the aerial parts of the plant. This vehicle is thus generally inert and it must be acceptable in agriculture, especially on the treated plant. The vehicle can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers and the like) or liquid (water, alcohols, especially butanol, and the like).

The surface-active agent can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surface-active agents. There may be mentioned, for example, salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, (especially alkylphenols or arylphenols), salts of esters of sulphosuccinic acids, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated phenols or alcohols, esters of fatty acids and of polyols, and the derivatives of the above compounds containing sulphate, sulphonate and phosphate functional groups. The presence of at least one surface-active agent is generally indispensable when the active material and/or the inert vehicle is/are not soluble in water and the carrier agent for application is water.

The compositions for agricultural use 5 according to the invention can thus contain the active material within very wide limits, ranging from 0.05% to 95% (by weight). Their surface-active agent content is advantageously of between 5% and 40% by weight. Except when otherwise indicated, the percentages given in this description, including the claims, are by weight.

These compositions according to the invention are themselves in fairly diverse, solid or liquid forms.

There may be mentioned, as forms of solid compositions, the powders for dusting (with an active material content which can range up to 100%) and the granules, especially those obtained by extrusion, by compacting, by spraying, by impregnation of a granulated vehicle, or by granulation from a powder (the active material content 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; it is also possible to use a composition comprising 50 g of active material and 950 g of talc; it is also possible to 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 milled and the mixture is applied by dusting.

There may be mentioned, as forms of liquid compositions or those intended to constitute liquid compositions at the time of application, solutions, in particular water-soluble concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or powder to be sprayed), pastes or gels.

Wettable powders (or powder to be sprayed) are generally prepared so that they contain 20 to 95% of active material, and they generally contain, in addition to the solid vehicle, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersing agent and, when this is necessary, from 0.1 to 10% of one or more stabilizing agents and/or other additives, such as penetrating agents, adhesives, or anticlumping agents, dyes, and the like.

To obtain powders to be sprayed or wettable powders, the active materials are intimately mixed, in suitable mixers, with the additional substances and the mixture is milled with mills or other suitable grinders. Powders to be sprayed are thereby obtained with advantageous wettability and suspensibility; they can be suspended in water at any desired concentration and these suspensions can be used very advantageously in particular for application to plant leaves.

Pastes can be produced in place of wettable powders. The conditions and modes of production and use of these pastes are similar to those of wettable powders or powders to be sprayed.

Various wettable powder (or powder to be sprayed) compositions are given here as examples:

WP Example 1 - active material ........... iii... 50% - ethoxylated fatty alcohol (wetting agent) . 2.5% - ethoxylated phenylethylphenol (dispersing = Fe = of J 5% - chalk (inert vehicle) .......... cc... 42.5%

WP Example 2: - active material ......c.ciiiiiiiiiiianaaa... 10% - C13 branched-type synthetic oxo alcohol, ethoxylated with 8 to 10 molecules of ethylene oxide (wetting agent) ............ 0.75% - neutral calcium lignosulphonate (dispersing agent) .......cuiiiiiinnnnea.. 12% - calcium carbonate (inert filler) .......gs for 100%

WP Example 3:

This wettable powder contains the same ingredients as in the above example, in the proportions below: - active material .........i.iiii iii. 15% - wetting agent ......... iii, 1.50% - dispersing agent .....i..iiiiie iii. 8% - calcium carbonate (inert filler) .......gs for 100%

WP Example 4: - active material .... i... ee eee. 90%

- ethoxylated fatty alcohol (wetting agent).. 4% - ethoxylated phenylethylphenol (dispersing = Lo = 0 wl 6%

WP Example 5: - active material ........... iii... 50% - mixture of anionic and nonionic surface- active agents (wetting agent) ............. 2.5% - sodium lignosulphonate (dispersing agent).. 5% - kaolin clay (inert vehicle) ............... 42.5%

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 contained within the general scope of the present invention.

Emulsions can be of the water-in-oil or oil-in-water type 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, which also come within the scope of the invention.

These dispersible granules, with a bulk density generally of between approximately 0.3 and 0.6, have a particle size generally of between approximately 150 and 2000 and preferably between 300 and 1500 microns.

The active material content of these granules is generally between approximately 1% and 90%, and preferably between 25% and 90%.

The rest of the granule is essentially composed of a solid filler and, optionally, of surface- active adjuvants which confer water-dispersibility properties on the granule. These granules can be essentially of two distinct types according to whether the filler held is soluble or insoluble in water. When the filler is water-soluble, it can be inorganic or, preferably, organic. Excellent results were obtained with urea. In the case of an insoluble filler, the latter is preferably inorganic, such as, for example, kaolin or bentonite. It is then advantageously accompanied by surface-active agents (in a proportion of 2 to 20% by weight of the granule) of which more than half consists of, for example, at least one dispersing agent, essentially anionic, such as an alkali metal or alkaline-earth metal polynaphthalenesulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali metal or alkaline-earth metal alkylnaphthalenesulphonate.

Moreover, although this is not indispensable, it is possible to add other adjuvants such as antifoaming agents.

The granule according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (granulator, fluid bed, sprayer, extrusion, and the like). The preparation generally finishes with a crushing followed by a sieving to the particle size chosen within the limits mentioned above. Granules obtained as above and then impregnated with a composition containing the active material can alternatively be used.

It is preferably obtained by extrusion, by carrying out the preparation as indicated in the examples below.

DG Example 1: Dispersible granules 90% by weight of active material and 10% of urea in the form of pearls are mixed in a mixer. The mixture is then milled in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The moist powder is extruded in a perforated-roller extruder. A granular material is obtained which is dried, and then crushed and sieved, 50 as to respectively keep only the granules with a size of between 150 and 2000 microns. :

DG Example 2: Dispersible granules

The following constituents are mixed in a mixer: - active material ........... iii. 15% - wetting agent {sodium alkylnaphthalene- sulphonate ... iii iti ete ees 2% - dispersing agent (sodium polynaphthalene-~ sulphonate) ... iii iit tite ieee 8%

- water-insoluble inert filler (kaolin) ..... 15%

This mixture is granulated on a fluid bed in the presence of water and then dried, crushed and sieved so as to obtain granules with a size of between 0.15 and 0.80 mm.

These granules can be used alone or in solution or dispersion in water so as to obtain the required dose. They can also be used to prepare combinations with other active materials, especially fungicides, the latter being in the form of wettable powders or granules or aqueous suspensions.

As regards the compositions which are suitable for storage and transportation, they more advantageously contain from 0.5 to 95% (by weight) of active material.

Another subject of the invention is a process for the curative or preventive control of fungi which are phytopathogenic, for example towards crops or lawns, characterized in that an effective and non- phytotoxic amount of a combination of at least one compound A and at least one compound B, for example in a fungicidal composition according to the invention, is applied on the aerial parts of plants.

The fungi which are phytopathogenic towards crops which can be combatted by this process are in particular those: - from the Oomycetes group: - from the Phytophthora genus, such as

Phytophthora infestans (downy mildew of the Solanaceae, in particular of potatoes or tomatoes), Phytophthora citrophthora, Phytophthora capsici, Phytophthora cactorum, Phytophthora palmivora, Phytophthora cinnamoni, Phytophthora megasperma or Phytophthora parasitica, - from the Peronosporaceae family, in particular Plasmopara viticola (grape downy mildew),

Plasmopara halstedei (sunflower downy mildew),

Pseudoperonospora sp (in particular downy mildew of cucurbits and of hops), Bremia lactucae (lettuce downy mildew) or Peronospora tabacinae (tobacco downy mildew), - from the family of the Pythiums, in particular Pythium ultimum, Pythium aphanidermatum,

Pythium sylvaticum, Pythium irregulare or Pythium arrheomales, - from the Adelomycetes group: - from the Alternaria genus, for example

Alternaria solani (alternaria disease of the Solanaceae and in particular of tomatoes and potatoes), - from the Guignardia genus, in particular Guignardia bidwellii (black rot of grapes), - from the Oidiums group, for example grape powdery mildew (Uncinula necator); powdery mildew of legumes, for example Erysiphe polygoni (powdery mildew of crucifers); Leveillula taurica, Erysiphe cichoracearum, Sphaerotheca fuligena; (powdery mildew of cucurbits, of composites or of tomatoes); Erysiphe communis (beet and cabbage powdery mildew); Erysiphe pisi (pea or lucerne powdery mildew); Erysiphe polyphaga (bean and cucumber powdery mildew); Erysiphe umbelliferarum (powdery mildew of the Umbelliferae, in particular of carrots); Sphaerotheca humuli (hop powdery mildew); or Erysiphe graminis (powdery mildew of cereals).

A classification made no longer by targeted fungi but by target crops can be illustrated as below: - grapes: powdery mildew (Uncinula necator), downy mildew (Plasmopara viticola), excoriosis (Phomopsis viticola) and black rot (Guignardia bidwellii), - Solanaceae: downy mildew (Phytophthora infestans), alternaria disease (Alternaria solani) and rot (Botrytis cinerea), - vegetable crops: downy mildews (Peronospora sp., Bremia lactucae, Pseudoperonospora sp. or alternaria disease (Alternaria sp.), sclerotinia disease (Sclerotinia sp.), rot (Botrytis cinerea) or powdery mildew (Erysiphe sp. or Sphaerotheca fuliginea), - arboriculture: scab (Venturia inaequalis), powdery mildew (Podosphaera leucotricha) and monilia disease (Monilia fructigena), - citrus fruits: scab (Elsinoe fawcetti), melanose (Phomopsis citri) and diseases due to Phytophthora sp., bananas: cercospora disease (Mycosphaerella figiensis) or root complex (Pythium sSp.), - lawns: rust, powdery mildew, helminthosporium disease or soil diseases (Microdochium nivale, Pythium sp., Rhizoctonia solani, and the like).

The fungicidal combination which is the subject of the invention is applied by means of various treatment processes, such as: - spraying the liquid comprising the said composition on the aerial parts of the crops to be treated, - dusting, the incorporation of granules or of powders into the soil, sprinkling, injecting into trees or painting.

The spraying of a liquid on the aerial parts of the crops to be treated is the preferred treatment process. "Effective and non-phytotoxic amount" is understood to mean an amount of composition according to the invention which is sufficient to make possible control or destruction of the fungi present or capable of appearing on the crops and which does not result in any significant phytotoxicity symptoms with respect to the said crops. Such an amount is capable of varying within wide limits depending on the fungi to be controlled, the type of crop, the weather conditions and the compounds included in the fungicidal composition according to the invention. This amount can be determined by systematic tests in the field, within the scope of the person skilled in the art.

The use doses during the implementation of the process according to the invention will then generally be: on grapes, vegetable crops, Solanaceae, bananas, arboriculture or citrus fruits: 500 to 5000 g/ha of compound B, for example fosetyl-Al, + 25 to 500 g/ha of compound A and more precisely 1000 to 3000 g/ha + 50 to 200 g/ha, i.e. a total dose of composition according to the invention of between 525 and 5500 g/ha, preferably between 1050 and 3200 g/ha, on lawns: 5000 to 25000 g/ha of compound B, for example fosetyl-Al, + 100 to 500 g/ha of compound A and more precisely 7000 to 20000 g/ha + 150 to 350 g/ha, i.e. a total dose of composition according to the invention of between 5100 and 25500 g/ha, preferably between 7150 and 20350 g/ha.

The following examples are given purely by way of illustration of the invention, which they do not limit in any way.

Example 1: In vivo test of the combination of (Ia) with fosetyl-Al with respect to Plasmopara viticola (grape downy mildew) by preventive treatment 72 hours before infection.

Materials and method.

The fungicides experimented on are as follows:

Compound A (IA - trifloxystrobin): in the form of pure active material,

Compound B: WG formulation containing 800 g of fosetyl-

Al/kg.

The fungicidal compositions experimented on are as follows:

Compound A (IA) at the doses of 32, 64 and 128 ppm,

Compound B at the doses of 160, 320, 640 and 1280 ppm of fosetyl-Al,

Compound A (IA) + Compound B at the doses of: 32+640 and 64+1280 ppm of Compound A (IA) + fosetyl-Al (A/B = 1/20), 32+320, 64+640 and 128+1280 ppm of Compound A (IA) + fosetyl-Al (A/B = 1/10), 32+160, 64+320 and 128+640 ppm of Compound A (IA) + fosetyl-Al (A/B = 1/5).

Vine seedlings (var. Chardonnay), aged 8 weeks, are treated with the fungicidal compositions at the doses cited above (3 repetitions of two seedlings/dose). They are inoculated three days later by spraying the lower face of the leaves with an aqueous suspension comprising 100,000 spores of

Plasmopara viticola/ml of inoculum. The seedlings are

Claims

1. Synergistic fungicidal composition comprising at least one compound A of formula (Ia) or (Ib): Me CF, WNC MeO _ ~ : ~N ~COOMe (1a) Me OCF, WSS MeQO_ ~— . ~N COOMs (Ib) ’ and at least one fungicidal compound B chosen from the group comprising derivatives of phosphorous acid and phosphorous acid itself and its alkali metal or alkaline-earth metal salts; the said composition comprising the components A and B in an A/B ratio by weight of between

0.004 and 1.

2. Fungicidal composition according to claim 1, ; characterized in that the fungicidal compound B is chosen from the group comprising metal phosphites and fosetyl-

Al.

3. Fungicidal composition according to either of claims 1 and 2, characterized in that the components A Amended Sheet 21/06/2002 and B are in an A/B ratio by weight of between 0.0075 and

0.2.

4. Fungicidal composition according to any one of claims 1 to 3, characterized in that the compound A is the compound of formula (Ia).

5. Fungicidal composition according to any one of claims 1 to 4, characterized in that the compound B is fosetyl Al.

6. Fungicidal composition according to claim 5, characterized in that the A/B ratio is between 0.005 and 1 for all the crops envisaged.

7. Fungicidal composition according to claim 5, characterized in that the A/B ratio is between 0.017 and

0.2 for all crops envisaged.

8. Fungicidal composition according to claim 5, characterized in that, in the case of lawns, the A/B ratio is between 0.004 and 0.1.

9. Fungicidal composition according to claim 5, characterized in that, in the case of lawns, the A/B ratio is between 0.0075 and 0.05.

10. Fungicidal composition according to any one of claims 1 to 9, characterized in that it comprises the compounds A and B as a mixture with the solid or liquid vehicles which are acceptable in agriculture and/or the surface-active agents which are also acceptable in agriculture.

11. Fungicidal composition according to any one of claims 1 to 10, characterized in that it comprises from 0.05 to 95% (by weight) of active material.

12. Process for controlling phytopathogenic fungi of a medium, characterized in that at least one compound A and at least one compound B are applied to the said medium, these compounds being as defined in claim 1 and : Amended Sheet 21/06/2002 the combination of these compounds being in an effective and non-phytotoxic total amount.

13. Process for the curative or preventive control of fungi which are phytopathogenic towards crops or lawns, characterized in that an effective and non- phytotoxic amount of a fungicidal composition according to any one of claims 1 to 11 is applied on the aerial parts of the plants.

14. Process for the control of fungi which are phytopathogenic towards crops according to claim 13, characterized in that a dose of between 525 and 5500 g/ha of composition is applied.

15. Process for the control of fungi which are phytopathogenic towards crops according to claim 13, characterized in that a dose of between 1050 and 3200 g/ha of composition is applied.

16. Process for the control of fungi which are phytopathogenic towards lawns according to claim 13, characterized in that a dose of between 5100 and 25500 g/ha of composition is applied.

17. Process for the control of fungi which are phytopathogenic towards lawns according to claim 13, characterized in that a dose of between 7150 and 20350 g/ha of composition is applied.

18. A product comprising at least one compound A as defined in claim 1 and at least one compound B as defined in claim 1 for the control of phytopathogenic fungi of a medium by simultaneous application. ’

19. A fungicidal composition according to claim 1 substantially as herein described with reference to any one of the illustrative Examples. Amended Sheet 21/06/2002