AU1399801A - Oligobenzimidazole derivatives and their use as dna transfection agents - Google Patents

Abstract

The invention concerns oligobenzimidazole derivatives capable of combining with nucleic acids of general formula (I) wherein: R represents a hydrogen atom or certain substituents; n is an integer equal to 2, 3, 4 or 5; and R' represents a -O-R3, -S-R3, NHR3 group or -O-CO-NH-R3 and R3 represents an alkyl group; or R' represents a -NR4R5 group or -O-CO-NR4R5 and R4 and R5 represent each an alkyl group, the alkyl radicals containing 12 to 22 carbon atoms; their salts, compositions containing them and their uses, for example for transferring <i>in vitro</i>, <i>in vivo</i> or <i>ex vivo</i> nucleic acids into cells or for visual display of nucleic acids administered by fluorescence.

Description

2 advantageous to be able to decrease the amount of chemicals distributed in the environment, while ensuring high-performance protection of crops against fungal attacks. 5 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 10 therefore, in first place, a synergistic fungicidal composition comprising at least one compound A of formula (Ia) or (Ib): Me c O -CF 3 N Meo N COOMe (1a) SMe

OCF

3 N Mo% N COOMe (Ib) 15 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 3 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, 5 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 10 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 15 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 20 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 25 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 4 following formula, also known as the Colby formula: E = X + Y - X.Y/100 in which: - E is the expected percentage of inhibition 5 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, 10 - 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 15 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. 20 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 25 Tomlin and published by The British Crop Protection Council, 11th edition, 1997; - l'Index phytosanitaire [Plant-protection index] 1998, published by l'Association de Coordination 5 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 10 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 15 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 20 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 25 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 6 vehicles and, optionally, one or more surface-active agents. In the present account, the term 'vehicle" denotes a natural or synthetic, organic or inorganic 5 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 10 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 15 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 20 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 25 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 7 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 10 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 15 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 20 (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 25 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 8 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 5 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) 10 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 15 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 20 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 25 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 9 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: 5 WP Example 1 - active material .. ........................... 50% - ethoxylated fatty alcohol (wetting agent) 2.5% - ethoxylated phenylethylphenol (dispersing agent) .... ................................... 5% 10 - chalk (inert vehicle) .. ..................... 42.5% WP Example 2: - active material .. ........................... 10% - C13 branched-type synthetic oxo alcohol, ethoxylated with 8 to 10 molecules of 15 ethylene oxide (wetting agent) .............. 0.75% - neutral calcium lignosulphonate (dispersing agent) .. ........................ 12% - calcium carbonate (inert filler) ....... qs for 100% WP Example 3: 20 This wettable powder contains the same ingredients as in the above example, in the proportions below: - active material .. ........................... 75% - wetting agent ... ............................ 1.50% 25 - dispersing agent ... ......................... 8% - calcium carbonate (inert filler) ....... qs for 100% WP Example 4: - active material ... .......................... 90% 10 - ethoxylated fatty alcohol (wetting agent).. 4% - ethoxylated phenylethylphenol (dispersing agent) .... ................................... 6% WP Example 5: 5 - active material .. ........................... 50% - mixture of anionic and nonionic surface active agents (wetting agent) ............... 2.5% - sodium lignosulphonate (dispersing agent).. 5% - kaolin clay (inert vehicle) ................ 42.5% 10 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. 15 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 20 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 25 150 and 2000 and preferably between 300 and 1500 microns. The active material content of these granules is generally between approximately 1% and 90%, and 11 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 5 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 10 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 15 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 20 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 25 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 12 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 5 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 10 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 15 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, so as to respectively keep only the granules with a 20 size of between 150 and 2000 microns. DG Example 2: Dispersible granules The following constituents are mixed in a mixer: - active material ............................. 75% 25 - wetting agent (sodium alkylnaphthalene sulphonate ... ............................... 2% - dispersing agent (sodium polynaphthalene sulphonate) .................................. 8% 13 - 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 5 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 10 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 15 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 20 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 25 crops which can be combatted by this process are in particular those: - from the Oomycetes group: - from the Phytophthora genus, such as 14 Phytophthora infestans (downy mildew of the Solanaceae, in particular of potatoes or tomatoes), Phytophthora citrophthora, Phytophthora capsici, Phytophthora cactorum, Phytophthora palmivora, Phytophthora 5 cinnamoni, Phytophthora megasperma or Phytophthora parasitica, - from the Peronosporaceae family, in particular Plasmopara viticola (grape downy mildew), Plasmopara halstedei (sunflower downy mildew), 10 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 15 particular Pythium ultimum, Pythium aphanidermatum, Pythium sylvaticum, Pythium irregulare or Pythium arrheomales, - from the Adelomycetes group: - from the Alternaria genus, for example 20 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 25 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 15 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 5 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 10 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), 15 - Solanaceae: downy mildew (Phytophthora infestans), alternaria disease (Alternaria solani) and rot (Botrytis cinerea), - vegetable crops: downy mildews (Peronospora sp., Bremia lactucae, Pseudoperonospora 20 sp. or alternaria disease (Alternaria sp.), sclerotinia disease (Sclerotinia sp.), rot (Botrytis cinerea) or powdery mildew (Erysiphe sp. or Sphaerotheca fuliginea), - arboriculture: scab (Venturia 25 inaequalis), powdery mildew (Podosphaera leucotricha) and monilia disease (Monilia fructigena), - citrus fruits: scab (Elsinoe fawcetti), melanose (Phomopsis citri) and diseases due 16 to Phytophthora sp., bananas: cercospora disease (Mycosphaerella figiensis) or root complex (Pythium sp.), 5 - 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 10 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 15 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. 20 "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 25 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 17 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. 5 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: 10 500 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 15 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 20 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 25 limit in any way. Example 1: In vivo test of the combination of (Ia) with fosetyl-Al with respect to Plasmopara viticola (grape 18 downy mildew) by preventive treatment 72 hours before infection. Materials and method. The fungicides experimented on are as 5 follows: Compound A (IA - trifloxystrobin): in the form of pure active material, Compound B: WG formulation containing 800 g of fosetyl Al/kg. 10 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, 15 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), 20 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 25 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 19 then placed in a controlled-environment chamber at 20oC, 100% RH (relative humidity) for 7 days. An assessment is then carried out. This consists in estimating the leaf surface area enduring a sporulating 5 infection (recognisable in the whiteish down) and, by comparison with an untreated/infected control, in defining the percentage of effectiveness according to the following formula: % practical effectiveness = 100 x (% Control 10 infection - % Test infection)/% Control infection The theoretical effectiveness according to the Colby formula is calculated from the following formula: % A+B theoretical effectiveness = % A practical eff. + 15 % B practical eff. - (% A practical eff. x % B practical eff./100) Results Practical effectiveness: Fosetyl-Al Compound A (IA) 0 160 320 640 1280 0 29 36 25 57 32 77 68 77 71 64 71 88 93 99 128 98 95 100 20 20 Theoretical effectiveness (Colby): Fosetyl-Al Compound A (IA) 0 160 320 640 1280 0 29 36 25 57 32 77 83 85 83 64 71 82 79 88 128 98 98 99 Synergy: Fosetyl-Al Compound A (IA) 0 160 320 640 1280 0 32 -16 -8 -11 64 6 14 12 128 -4 1 5 The combination with fosetyl-Al makes it possible to obtain a modest synergistic relationship when 64 ppm of trifloxystrobin are combined with 640 or 1280 ppm of fosetyl-Al (ratios 1/10 and 1/20). 10 Example 2: In vivo test of the combination of (Ib) with fosetyl-Al with respect to Plasmopara viticola (grape downy mildew) by preventive treatment 72 hours before infection. Materials and method. 15 The fungicides experimented on are as 21 follows: Compound A (IB): in the form of pure active material, Compound B: WG formulation containing 800 g of fosetyl Al/kg. 5 The fungicidal compositions experimented on are as follows: Compound A (IB) at the doses of 8, 16 and 32 ppm, Compound B at the doses of 80, 160, 320 and 640 ppm of fosetyl-Al, 10 Compound A (IB) + Compound B at the doses of: 8+160, 16+320 and 32+640 ppm of Compound A (IB) + fosetyl-Al (A/B = 1/20), 8+80, 16+160 and 32+320 ppm of Compound A (IB) + fosetyl-Al (A/B = 1/10), 15 16+80 and 32+160 ppm of Compound A (IB) + 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 20 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 then placed in a controlled-environment chamber at 25 20 0 C, 100% RH (relative humidity) for 7 days. An assessment is then carried out. This consists in estimating the leaf surface area enduring a sporulating infection (recognisable in the whitish down) and, by 22 comparison with an untreated/infected control, in defining the percentage of effectiveness according to the following formula: % practical effectiveness = 100 x (% Control 5 infection - % Test infection)/% Control infection The theoretical effectiveness according to the Colby formula is calculated from the following formula: % A+B theoretical effectiveness = % A practical eff. + 10 % B practical eff. - (% A practical eff. X % B practical eff./100) Results Practical effectiveness: Fosetyl-Al Compound A (IB) 0 80 160 320 640 0 24 17 7 14 8 24 24 38 16 21 31 31 57 32 38 51 52 86 23 Theoretical effectiveness (Colby): Fosetyl-Al Compound A (IB) 0 80 160 320 640 0 24 17 7 14 8 24 42 37 16 21 40 34 26 32 38 49 42 46 Synergy: Fosetyl-Al Compound A (IB) 0 80 160 320 640 0 8 -18 1 16 -9 -3 31 32 2 10 40 5 A synergistic relationship is noticed as soon as the activity becomes significant (>50%). This relationship is the most marked when 16 ppm of Ib is combined with 320 ppm of fosetyl-Al (ratio 1/20) or 10 32 ppm of Ib with 320 or 640 ppm of fosetyl-Al (ratios 1/10 and 1/20). The most clear-cut synergy relates to the ratio 1/20.

Claims (13)

1. Synergistic fungicidal composition comprising at least one compound A of formula (Ia) or 5 (Ib): Me CF 3 ON N MeO~ N COOMe (1a) Me OCF 3 N MeO / N COOMO (Ib) and at least one fungicidal compound B chosen from the group comprising derivatives of phosphorous 10 acid, for example metal phosphites, such as fosetyl-Al, 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 15 0.004 and 1, preferably between 0.0075 and 0.2.

2. Fungicidal composition according to claim 1, characterized in that the compound A is the compound of formula (Ia).

3. Fungicidal composition according to 25 either of claims 1 to 2, characterized in that the compound B is fosetyl Al.

4. Fungicidal composition according to any one of claims 1 to 3, characterized in that the A/B 5 ratio is between 0.005 and 1, preferably between 0.017 and 0.2, for all the crops envisaged.

5. Fungicidal composition according to any one of claims 1 to 3, characterized in that, in the case of lawns, the A/B ratio is between 0.004 and 0.1, 10 preferably between 0.0075 and 0.05.

6. Fungicidal composition according to any one of claims 1 to 5, characterized in that it comprises the compounds A and B as a mixture with the solid or liquid vehicles which are acceptable in 15 agriculture and/or the surface-active agents which are 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 20 material.

8. 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 25 claim 1 and the combination of these compounds being in an effective and non-phytotoxic total amount.

9. Process for the curative or preventive 26 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 7 is applied on the 5 aerial parts of the plants.

10. Process for the control of fungi which are phytopathogenic towards crops according to claim 9, characterized in that a dose of between 525 and 5500 g/ha, preferably between 1050 and 3200 g/ha, of 10 composition is applied.

11. Process for the control of fungi which are phytopathogenic towards lawns according to claim 9, characterized in that a dose of between 5100 and 25500 g/ha, preferably between 7150 and 20350 g/ha, of 15 composition is applied.

12. 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 20 application. """ "..J P...NOW, rM PCT/FR 99/03249 PaW* do aNmu Pdication Paent family Picanon naed in oah uol - date membete) dde W0 9703563 A 06-02-1997 FR 2737086 A 31-01-1997 AU 715861 B 10-02-2000 AU 6662896 A 18-02-1997 BR 9609798 A 16-03-1999 CA 2224890 A 06-02-1997 CN 1193890 A 23-09-1998 EP 0841853 A 20-05-1998 HR 960351 A 28-02-1998 HU 9901394 A 30-08-1999 JP 11511125 T 28-09-1999 US 6015802 A 18-01-2000 EP 0460575 A 11-12-1991 CH 689421 A 15-04-1999 AT 143003 T 15-10-1996 AT 182880 T 15-08-1999 AU 633736 B 04-02-1993 AU 7816791 A 12-12-1991 CA 2043733 A 06-12-1991 CS 9101688 A 15-01-1992 DE 69108191 D 24-10-1996 DE 59109146 D 09-09-1999 DK 460575 T 07-10-1996 EP 0703215 A 27-03-1996 EP 0694529 A 31-01-1996 EP 0893434 A 27-01-1999 ES 2091834 T 16-11-1996 8R 3021080 T 31-12-1996 HK 1005721 A 22-01-1999 HU 57541 A 30-12-1991 IE 80848 B 07-04-1999 IL 98341 A 16-10-1996 JP 4235953 A 25-08-1992 LV 10609 A 20-04-1995 LV 10609 B 20-04-1996 NZ 238346 A 24-02-1995 PL 168218 B 31-01-1996 PT 97848 A,B 31-03-1992 SG 42939 A 17-10-1997 SK 278282 B 07-08-1996 RU 2077527 C 20-04-1997 KR 172948 B 30-03-1999 LT 1709 A,B 25-07-1995 MX 26077 A 01-10-1993 ZA 9104221 A

25-03-1992 WO 9700011 A 03-01-1997 AU 709776 B 09-09-19 AU 6300096 A 15-01-1997. BR 9608356 A 18-08-1998 CA 2221759 A 03-01-1997 CZ 9704041 A 13-05-1998 EP 0831697 A 01-04-1998 HU 9801819 A 30-11-1998 JP 11507654 T 06-07-1999 PL 323677 A 14-04-1998 US 6011064 A 04-01-2000 ZA 9605081 A 17-12-1996 EP 0741970 A 13-11-1996 J? 7157403 A 20-06-1995 page 1 of 2 PCT/FR 99/03249 Past e~ Pisoaon Pawnt family PtNeation fd In o.Mm rpodt memiber(s) dae EP 0741970 A JP 7187917 A 25-07-1995 JP 7285811 A 31-10-1995 JP 7285812 A 31-10-1996 JP 7304607 A 21-11-1995 JP 7304606 A 21-11-1995 JP 7316004 A 05-12-1995 JP 7324008 A 12-12-1995 JP 8026920 A 30-01-1996 JP 8026912 A 30-01-1996 AU 1120495 A 19-06-1995 W40 9515083 A 08-06-1995 W0 9740671 A 06-11-1997 AU 2696697 A 19-11-1997 amPsameAS1o ~pseuemirampg (M2 of2 page 2 of 2 IPCT/FR 99/03249 IAC 7 AMiN 7 0 "T/rAI01N37/50,69:26,57:12) Accor*hg wintemdoal Patent Cassioegen (IPO) or a bot nional deskilinen and IPC __________ S. naios UsAncHED tnman domanansW mmmmhd (easWIlMOefl system towe6d by ilaiUsn syne;ts) IPC 7 AO1N 0oasnmi tefl ahed wer tww mbman damfnrman w s ex ext via su domuns ar inded in *a o.se emue Becoso dase bmOaristed dmIing tw b1emYona buas (nmaa of d- be'se end. uwe priinL, hoi wad)m C. DOMTS NDERED TO BE R.LVANT_ Catgry Chokn di doamnumnt, xsi t aamftn we ppphmof ow reiut pags elevn d N& Y WO 97 03563 A (RHONE POULENC AGROCHIMIE 1-12 ;DUVERT PATRICE (FR)) 6 February 1997 (1997-02-06) page 1, line 4 - line 7 page 1, line 30 -page 2, line 19 Y DATABASE CROPU 'Online! 1-12 STN-Internati onal STN-accession no. 1998-88914, P.CLOUD ET AL.: 'Use of trifloxystrobin on peanuts, cucurbits, and other vegetables" XP002114955 abstract & PHYTOPATHOLOGY, vol. 88, no. 9 supply , 1998, page s18 -/ Funhr danunts ydadn con1w uwdne box C. X Paeft nliy meinbowe Ided In x. 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IiS Ptwrihu' Tx.51 51 ed.Lamers, W FaE (81-70)a 40-016 .sw pecrmeusse 4...anse )o w wa's page 1 of 2 PCT/FR 99/03249 C.(nWn)E DOoCUMNTB CMIUDEfEDTOD E REAN_ danw * Citagn er dominant. ann hiulma.where popqia l t theievarl passage RelvatW to ha No. Y DATABASE CROPU 'Online! 9 STN-International STN-accssion no. 1998-89706, A.TALLY ET AL.: "CGA-279202 - a new strobilurin fungicide from Novartis Crop Protection" XP002114956 abstract & PHYTOPATHOLOGY, vol. 88, no. 9 supply , 1998, page s88 Y EP 0 460 575 A (CIBA GEIGY AG) 1-12 11 December 1991 (1991-12-11) cited in the application examples 12,138 A WO 97 00011 A (CIBA GEIGY AG ;KNAUF BEITER 1-12 GERTRUDE (DE); ZEUN RONALD (DE)) 3 January 1997 (1997-01-03) the whole document A DATABASE CABA 'Online! 1-12 STN-International STN-accession no. 1999:16640, P.MARGOT ET AL.: "CGA 279202: a new broad-spectrum strobilurin fungicide" XP002114957 abstract & BRIGHTON CROP PROTECTION CONFERENCE: PESTS & DISEASES - 1998: VOLUME 2: PROCEEDINGS OF AN INTERNATIONAL CONFERENCE, BROGHTON, UK, 16-19 NOVEMBER 1998, vol. 2, 1998, pages 375-382, A EP 0 741 970 A (SUMITOMO CHEMICAL CO) 1-12 13 November 1996 (1996-11-13) page 2, line 20 - line 35 page 2, line 38 A WO 97 40671 A (CIBA GEIGY AG ;ZEUN RONALD 1-12 (DE)) 6 November 1997 (1997-11-06) page 1, paragraph 2 -page 2, paragraph 1 page 2 of 2 oe~n Pr~momwoon " PCT/FR 99/03249 Paut dao PmIimo Pa funNy pihIawn dWs i "afdI mpW dMemmbi. do* EP 0741970 A Jf 7187917 A 25-07-1995 JP 7285811 A 31-10-1995 J! 7285812 A 31-10-1995 JP 7304607 A 21-11-1995 JP 7304606 A 21-11-1995 JP 7316004 A 05-12-1995 JP 7324008 A 12-12-1995 JP 8026920 A 30-01-1996 JP 8026912 A 30-01-1996 AU 1120495 A 19-06-1995 WO 9515083 A 08-06-1995 WO 9740671 A 06-11-1997 AU 2696697 A 19-11-1997 FtWMMOWAI (PW W*=page 2 of 2 oDm e In.Wase. N PCT/FR 99/03249 C44ufI) COMMENTS CONIDERES CoMME ER1 NM bwpr, nIan 11H . - mw&ns ei.e, we - 6e~samwrsiMdondm pm.s psranns n wdm.,wneioa ... Y DATABASE CROPU 'Online! 9 STN-International STN-accession no. 1998-89706, A.TALLY ET AL.: "CGA-279202 - a new strobilurin fungicide from Novartis Crop Protection' XP002114956 abr6g6 & PHYTOPATHOLOGY, vol. 88, no. 9 supply , 1998, page s88 Y EP 0 460 575 A (CIBA GEIGY AG) 1-12 11 dkcembre 1991 (1991-12-11) cit& dans la demanded exemples 12,138 A WO 97 00011 A (CIBA GEIGY AG ;KNAUF BEITER 1-12 GERTRUDE (bE); ZEUN RONALD (DE)) 3 janvier 1997 (1997-01-03) le document en enter A DATABASE CABA 'Online! 1-12 STN-4iternatl onal STN-accession no. 1999:16640, P.NARGOT ET AL.: "CGA 279202: a new broad-spectrum strobilurin fungicide" XP002114957 abrEg6 & BRIGHTON CROP PROTECTION CONFERENCE: PESTS & DISEASES - 1998: VOLUME 2: PROCEEDINGS OF AN INTERNATIONAL CONFERENCE, BROGHTON, UK, 16-19 NOVEMBER 1998, vol. 2, 1998, pages 375-382, A EP 0 741 970 A (SUMITOMO CHEMICAL CO) 1-12 13 novembre 1996 (1996-11-13) page 2, ligne 20 - ligne 35 page 2, ligne 38 A WO 97 40671 A (CIBA GEIGY AG ;ZEUN RONALD 1-12 (DE)) 6 novembre 1997 (1997-11-06) page 1, alin6a 2 -page 2, alinda 1 1 Puwu#e, PenI1.<~ .6, a aan..) Q'dist 10 PCT/FR 99/03249 Poledt docomuwr Ptiosuion Patmnitfandy ftkallon died I "uuch report da Moreus) dmo NO 9703653 A 06-02-1997 FR 2737086 A 31-01-1997 AU 715861 B 10-02-2000 AU 6662896 A 18-02-1997 BR 9609798 A 16-03-1999 CA 2224890 A 06-02-1997 CN 1193890 A 23-09-1998 EP 0841853 A 20-05-1998 HR 960351 A 28-02-1998 HU 9901394 A 30-08-1999 JP 11511125 T 28-09-1999 US 6015802 A 18-01-2000 EP 0460575 A 11-12-1991 CH 689421 A 15-04-1999 AT 143003 T 15-10-1996 AT 182880 T 15-08-1999 AU 533735 8 04-02-1993 AU 7816791 A 12-12-1991 CA 2043733 A 06-12-1991 CS 9101688 A 15-01-1992 DE 59108191 D 24-10-1996 DE 59109146 0 09-09-1999 DK 460575 T 07-10-1996 EP 0703215 A 27-03-1996 EP 0694529 A 31-01-1996 EP 0893434 A 27-01-1999 ES 2091834 T 16-11-1996 GR 3021080 T 31-12-1996 HK 1005721 A 22-01-1999 HU 57541 A 30-12-1991 IE 80848 B 07-04-1999 IL 98341 A 16-10-1996 JP 4235953 A 25-08-1992 LV 10609 A 20-04-1995 LV 10609 B 20-04-1996 NZ 238346 A 24-02-1995 PL 168218 B 31-01-1996 PT 97848 AB 31-03-1992 SG 42939 A 17-10-1997 SK 278282 8 07-08-1996 RU 2077527 C 20-04-1997 KR 172948 B 30-03-1999 LT 1709 A,B 25-07-1995 MX 26077 A 01-10-1993 ZA 9104221 A 25-03-1992 NO 9700011 A 03-01-1997 AU 709775 B 09-09-1999 AU 6300096 A 15-01-1997 BR 9608356 A 18-08-1998 CA 2221759 A 03-01-1997 CZ 9704041 A 13-05-1998 EP 0831697 A 01-04-1998 HU 9801819 A 30-11-1998 JP 11507654 T 06-07-1999 PL 323677 A 14-04-1998 US 5011064 A 04-01-2000 ZA 9605081 A 17-12-1996 EP 0741970 A 13-11-1996 JP 7157403 A 20-06-1995 Pam poTrsAM@ IP ~wm*pg ofM 2 page 1of 2 Am iv-mwft a Bomb Iumom " PCT/FR 99/03249 Douwgd btx d* o Membr*) do In OM.t dt ou- p thdo dr~ idu faidis do brswtKs) otmmdmo EP 0741970 A JP 7187917 A 25-07-1995 JP 7285811 A 31-10-1995 JP 7285812 A 31-10-1995 JP 7304607 A 21-11-1995 JP 7304606 A 21-11-1995 JP 7316004 A 05-12-1995 JP 7324008 A 12-12-1995 JP 8026920 A 30-01-1996 JP 8026912 A 30-01-1996 AU 1120495 A 19-06-1995 WO 9515083 A 08-06-1995 WO 9740671 A 06-11-1997 AU 2696697 A 19-11-1997 page 2 de 2 wun - "m IPCT/FR 9g/03249 7IBA U~g~vo76!N37/5Q,537609:26,7: 12) Udu~Iae~emii b~~egd~dmbrw w b Ol)m II d. den is daedi~eng-denal ad lOl L OOUDEU* SUN LULS LA RECHCHE A PORE ;DUVERT PATRICE (FR)) 6 f6vrler 1997 (1997-02-06) page 1, ligne 4 - ligne 7 page 1, ligne 30 -page 2, llgne 19 Y DATABASE CROPU 'Onlinet 1-12 STN-Internatl onal STN-accession no. 1998-88914, P.CLOJD ET AL.: "Use of trifloxystrobin on peanuts, cucurbits, and other vegetables" XPOO2114955 abrdg6 & PHYTOPATHOLOGY, Vol. 88, no. 9 suppi.., 1998, page SIB Vdr lb madu s"~ C pemrl k An d Is Is 4.. doaftraf Lm. dommorftnd ali dw~o 4.brwa w 1n ampin uwww W ~deawtI*iap4w.l dmwd&.~~6 fm hmen ma lb ouu Imb..,4.flndo*en TV6UW deaisart WK uv u SWN6 5 lb di. 4. d~gw d invni doaw. ap~emi eulnt Twmnt W610 ruiqa.np L deii~.Wpm'ut ~b i 4b ~itIWsimom d4. biwnv perrut ma dorsmset (twnidiI lw =0 ee Z0i :ufw &ww= (tooEe wwhe 60 fm ge *kme0 Idoonint nw * fir 4su osV "t *"on ou usw a&" mnw &wnuft do mkn. nox.. otft awnkW*lbai 4i dt. *P deo0aftpaVU *vu Is f 1~ 1odm ~g4,1 ffo pEW um~1 poorW mdse peuisuwnwt&lbdi a pdolt mvendmiie W dammn qid Wal rai. do k nme fwlI dob~u D* & laqsW. lik eehmuie a ~dwwdes a fteffetvemat wimv5.si dz di 6owsi repsat 4.,ui%.di m w 5 avril 2000 12/04/2000 Nonmatade~ peW.d do rmdwm*%imchwqay6.dab. edxewmI gomwil Pfo o mwwUmu~w4dv*to 01e xmdee uWAW. 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