FR2596954A2 - Fungicide resulting from the combination of a compound possessing triazole and oligoether groups and of another fungicidal product - Google Patents

Abstract

The present certificate of addition to Patent Application No. 85.19194 relates to the combination of the compounds of formula I claimed in the said Patent Application with one or more products known for their fungicidal activity and chosen from the following subclasses: chlorinated or nitrated benzene derivatives, dicarboximide derivatives, derivatives comprising one or more heterocycles, derivatives of phosphorous acid, derivatives of dithiocarbamic acid, derivatives of phenol, derivatives of quinones, derivatives of carbamic acid and benzimidazoles, and sulphur-containing derivatives. The compounds/product weight ratio is generally between 0.0003 and 3000. Use of the combinations as fungicides.

Description

 The present invention, which is a first addition certificate to main application No. 85.19194, relates to a novel compound for phytosanitary use with triazole and oligoether groups and combinations of this product with certain fungicides. The invention also relates to processes for the preparation of said compound as well as the application for the protection of plants, especially in the context of the fight against parasitic fungi but also the growth regulation of plants of said compound and said associations.

 Many triazole compounds, especially fungicides, are already known in particular from European Patent Application No. 151084.

 An object of the invention is to provide compounds and combinations having improved activity and / or selectivity.

 Another object of the invention is to provide compounds and combinations that can be used not only against fungal attacks of cereals but also against fungal attacks on vines and arboriculture and vegetable crops.

 Another object of the invention is to provide compounds and combinations with reduced toxicological risks compared with certain known products.

ainsi que les sels acceptables en agriculture de ce composé.It has now been found that these goals can be achieved on the one hand by virtue of the compound of the invention which has the formula

as well as the agriculturally acceptable salts of this compound.

 The compound according to the invention can exist in two forms of diastereoisomers. The invention thus relates both to a mixture of the two diastereoisomeric forms and to the two diastereoisomers taken separately. The separation of the diastereoisomers can be carried out according to the methods known per se.

 The invention also relates to the salified forms of the compound according to the invention and more particularly the hydrochloride, sulphate, oxalate, nitrate or arylsulphonates as well as the complexes of addition of this compound with metal salts, and in particular iron salts, chromium , copper, manganese, zinc, cobalt, tin, magnesium and aluminum. All the products consisting of the product of formula (I), its diastereoisomers and its derivatives are hereinafter referred to by the expression, in the plural: the compounds according to the invention.

 It has also been found that the aforementioned aims can be achieved by combining one or more compounds of formula (I) with at least one fungicide of group (II), that is to say a fungicide chosen from the Subclasses 1. Chlorinated or nitrated derivatives of benzene such as quintozene or chlorothalonil, 2. Dicarboximide derivatives such as captan, folpel, captafol, iprodione, procymidone, 3. Derivatives comprising one or more heterocycles such as quinolines, morpholines, 4. Phosphorous acid derivatives such as metal phosphites, 5. Derivatives of dithiocarbamic acid such as maneb or mancozeb, 6. Phenol derivatives such as dinocap, 7. Derivatives of quinones such as dithianon, 8.carbamic acid derivatives and benzimidazoles such as carbendazim, benomyl, thiophanate-methyl, 9. sulfur-containing derivatives, 10. amines and amides such as dichloran, carboxin, triforine, cymoxanil, metalaxyl, ofurace, 11. Diazines such as chinomethionate, fenarinol, anilazine, 12. Sulfonamides such as dichlofluanid, 13. Guanidines such as doguadine.

The active ingredients of group (II) are known active ingredients, most of them being described in detail in such works as "The
Pesticidal Manual "edited by" The British Crop Protection
Council "whose 7th edition dates from 1983.

 The combinations according to the invention are most often of the binary type (only one active substance of group II), but sometimes ternary (2 active group II) or quaternary (3 active group II) combinations are also used.

 Among the active ingredients, those selected from subclasses 1, 2, 3, 4, 5, 6, 7, 8, 9 will be preferred.

 Among the active substances of group II, the following active ingredients will be preferred chlorothalonil, iprodione, fenpropimorph, tridemorph, dinocap, dithianon, maneb, mancozeb, phosethyl-Al, captan, carbendazim, captafol, sulfur.

 The chemical names of the products listed above are given in the table annexed according to the English nomenclature. That is, with the indication of the position of the substituents placed before it.

 The weight ratio of the compound according to the invention with the active ingredients of group II described above is preferably between 0.0003 and 3000 and advantageously between 0.001 and 1000.

 The present invention also relates to methods for preparing the compounds according to the invention. Several of these methods are described in European Patent Application No. 151084, the substance of which is incorporated herein by reference.

dans laquelle Z est un atome de chlore ou de brome, avec un dérivé alcalin (par exemple un sel de sodium ou de potassium), ou un dérivé d'ammonium ou phosphonium quaternaires) du triazole.According to a first method, a compound of formula

wherein Z is a chlorine or bromine atom, with an alkaline derivative (for example a sodium or potassium salt), or a quaternary ammonium or phosphonium derivative) of triazole.

 The reaction is usually carried out in aprotic polar solvent medium and can also be catalyzed, for example by the addition of alkaline iodide; the temperature is generally between 50 and 2500C, preferably between 70 and 230OC. For economic reasons, overall concentrations of reagents of between 1 and 50% are most often used.

en présence d'un catalyseur acide, ayant la même signification que précédemment et R3 étant un radical organique, de préférence alkyle inférieur (C14), deux radicaux R3 pouvant constituer ensemble un radical organique divalent, de préférence alkylène inférieur.The compounds of formula (II) can be prepared by reaction of the alcohol CF 3 -CH 2 OH (trifluoroethanol) with a compound of formula

in the presence of an acid catalyst, having the same meaning as above and R3 being an organic radical, preferably lower alkyl (C14), two radicals R3 may together form a divalent organic radical, preferably lower alkylene.

 The catalyst acid used in this reaction may be a protic or aprotic acid. Protic acids that may be mentioned include hydrochloric acid, sulfuric acid, trifluoroacetic acid, perchloric acid, benzenesulfonic acid, toluenesulfonic acid and methanesulfonic acid.

As aprotic acids include Lewis acids such as BF3, Ale13 and SnC14. When hydrochloric acid is used as a catalyst, the latter can be generated in situ, for example using acyl chloride, and especially acetyl chloride, which reacts with the alcohol present to give birth to HC1.

 The reaction is usually carried out by simply heating the indicated reagents. The temperature is generally in the temperature range from 50 ° C. to the boiling temperature of the reaction medium.

Trifluoroethanol usually acts as a solvent in the reaction medium. An inert cosolvent may also be added, including an aliphatic hydrocarbon, alicyclic or aromatic, halogenated or not, or an ether.

 The compounds of formula (III) are prepared according to methods known per se.

en présence d'un catalyseur acide. Les divers symboles indiqués pour les formules de ces deux réactifs ont les significations données plus haut. Comme catalyseur acide on peut également utiliser ceux définis plus haut à propos de la préparation des composés de formule (Il). Les autres conditions réactionnelles sont aussi semblables à celles définies pour la préparation de ces composés de formule (lita). According to another process for the preparation of compounds according to the invention, trifluoroethanol (CF 3 -CH 2 OH) is reacted with a compound of formula

in the presence of an acid catalyst. The various symbols indicated for the formulas of these two reagents have the meanings given above. As acidic catalyst can also be used those defined above for the preparation of compounds of formula (II). The other reaction conditions are also similar to those defined for the preparation of these compounds of formula (lita).

 The compounds of formula (IV) can be obtained according to methods known per se.

 The combinations are prepared by simply mixing the desired products and compounds.

 The present invention also relates to the use of the compounds of formula (I) and previously defined combinations as a fungicide.

 The compounds and combinations according to the invention can therefore be used for both preventive and curative control against fungi, in particular of the basidiomycete, ascomycete, adelomycete or fungi-imperfecti type, in particular rust, powdery mildew, tramp-on, fusarium, Helminthosporiosis, septoria, rhizoctonia of plants and plants in general and in particular cereals such as wheat, barley, rye, oats and their hybrids and also rice and maize.

The compounds according to the invention are active in particular against the fungi mentioned in the European application 151084. They are also and still active against the following fungi: Acrostalagmus koningi, Alternaria, Colletotrichum, Corticium rolfsii,
Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Hormodendron cladosporioides, Lentinus degener or tigrinus, Lenzites quercina, Memnoniella echinata,
Myrothecium verrucaria, Paecylomyces varioti, Pellicularia sasakii, Phellinus megaloporus, Polystictus sanguineus,
Poria vaporaria, Sclerotium rolfsii, Stachybotris atra,
Stereum, Stilbum sp. Trametes trabea, Trichoderma pseudokoningi, Trichothecium roseum.

 The compounds and the combinations of the invention are especially interesting because of their wide spectrum in terms of cereal diseases (oidium, rust, trampling, helminthosporiosis, septoria, and especially hard-to-fight fusariosis). They are also of great interest because of their activity on botrytis and black Sigatoka, and therefore they can be applied to crops as varied as vine, market gardening and arboriculture, and tropical crops such as peanut, banana, coffee, palm, coconut, pecan and others.

 Finally, they exhibit excellent selectivity with respect to the cultures.

In addition to the applications already described above, the products according to the invention also have an excellent biocidal activity with regard to many other varieties of microorganisms among which may be mentioned, without limitation, fungi such as those of the genera - Pullularia as P. Pullulans, - Chaetomium as C. globosum, - Aspergillus as Aspergillus niger, - Coniophora as C. Puteana,
Because of their biocidal activity, the products of the invention make it possible to effectively combat the microorganisms whose proliferation creates many problems in the agricultural and industrial fields. For this purpose, they are particularly suitable for the protection of plants or products. industrial products such as wood, leather, paints, paper, ropes, plastics, industrial water circuits;
They are particularly well suited to the protection of timber products, especially wood, whether it is wood for furniture, timber or weather-exposed wood such as fence woods, vine pickets, railway sleepers.

 The compounds or combinations according to the invention used, alone or in the form of compositions as defined above, in the wood treatments may be optionally combined with one or more known biocidal products such as pentachlorophenol, metal salts, in particular copper, manganese, cobalt, chromium, zinc derived from mineral or carboxylic acids (heptanoic, octanoic, naphthenic acids); organic complexes of tin, mercaptobenzothiazole.

 They generally apply at doses of 0.005 to 5 kg / ha, preferably at doses of 0.01 to 5 kg / ha, preferably 0.05, more specifically 0.1 to 2 kg / ha.

 The use of at least one of the compounds of formula (I) in combination with iprodione is particularly advantageous in the treatment of diseases of cereals and seeds as well as in the treatment of leaf diseases.

 The use of at least one of the compounds of formula (I) in combination with carbendazim is particularly advantageous in the treatment of diseases of fruit and fruit trees, vegetable crops and cereals.

 The use of at least one of the compounds of formula (I) in combination with captafol is particularly advantageous in the treatment of diseases of cereals, fruit trees and fruit, potato.

 The use of at least one of the compounds of formula (I) in combination with captan is particularly advantageous in the treatment of diseases of cereals, fruit trees and fruits.

 The use of at least one of the compounds of formula (I) in combination with fenpropimorph is particularly advantageous in the treatment of cereal and beet diseases.

 The use of at least one of the compounds of formula (I) in combination with the tridemorph is particularly advantageous in the treatment of cereal diseases.

 The use of at least one of the compounds of formula (I) in combination with chlorotalonil is particularly advantageous in the treatment of diseases of vegetable crops, cereals, beets and potatoes.

 The use of at least one of the compounds of formula (I) in combination with maneb is particularly advantageous in the treatment of diseases of vegetable crops, fruit trees and fruits.

 For their practical use, the compounds and combinations according to the invention are rarely used alone. Most often they are part of compositions. These compositions, which can be used for the protection of plants against fungal diseases, or in plant growth regulating compositions, contain as active ingredient a compound according to the invention as described above in association with solid or liquid carriers, which are acceptable in agriculture and / or surfactants also acceptable in agriculture.

In particular, the usual inert carriers and surfactants are usable.

 By the term "carrier" in the present specification means an organic or inorganic material, natural or synthetic, with which the active ingredient is associated to facilitate its application on the plant, on seeds or on the ground. This support is therefore generally inert and must be acceptable in agriculture, especially on the treated plant. The support may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases , etc ...).

 The surfactant may be an emulsifier, dispersant or wetting agent of ionic or nonionic type. There may be mentioned, for example, salts of polyacrylic acids, salts of lignosulfonic 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 sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols. The presence of at least one surfactant is generally indispensable when the active ingredient and / or the inert carrier are not soluble in water and the application carrier agent is water.

 For their application, the compounds of formula (I) and the associations are therefore generally in the form of compositions; these compositions according to the invention are themselves in fairly diverse forms, solid or liquid.

 As forms of solid compositions, mention may be made of dusting or dispersion powders (with a content of compound of formula (I) 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 compound of formula (I) in these granules being between 1 and 80% for the latter cases).

 As forms of compositions which are liquid or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols and powders. wettable (or powder spray), pasta.

 These compositions may also contain any other kind of ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, etc. other known active substances with pesticidal properties (in particular insecticides or fungicides) or with properties promoting the growth of plants (in particular fertilizers) or with properties regulating the growth of plants. More generally, the compounds according to the invention can be combined with any solid or liquid additive corresponding to the usual techniques of formulation.

 These use doses in the case of fungicidal use of the compounds and combinations according to the invention may vary within wide limits, in particular according to the virulence of the fungi and the climatic conditions.

 In general, compositions containing 0.5 to 5000 ppm of active substance are suitable; these values are indicated for ready-to-use compositions. Ppm means "part by million". The zone from 0.5 to 5000 ppm corresponds to a zone of 5 × 10 to 0.5% (percentages by weight).

 As regards the compositions adapted for storage and transport, they more preferably contain from 0.5 to 95% (by weight) of active substance.

 Thus, the compositions for agricultural use according to the invention can contain the active ingredients according to the invention within very wide limits, ranging from 5.10 5% to 95% (by weight).

 In general, the compositions according to the invention usually contain from about 0.05 to about 95% of active ingredients (formula I and group II) according to the invention, from about 1% to about 95% of one or more solid carriers. or liquids and optionally from 0.1 to 50%, preferably from 5 to 40%, of about one or more surfactants.

 The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.01 to 20% of active material. In addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% of suitable additives, such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, colorants, adhesives mentioned above.

As an example, here is the composition of some concentrates
Example F (Formulation) 1 - Active Ingredient 400 g / l - Alkaline Dodecylbenzene Sulfonate 24 g / l - Nonylphenol Oxyethylated to 10 Molecules
of ethylene oxide 16 g / l - cyclohexanone 200 g / l - aromatic solvent qs 1 liter
According to another formula of emulsifiable concentrate, use is made of:
Example F 2: active ingredient 250 g, epoxidized vegetable oil 25 g, mixture of alkylaryl sulphonate and
of polyglycol ether and fatty alcohols 100 g - dimethyltormamide 50 g - xylene 575 g
From these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to the leaves.

 The concentrated suspensions, also applicable in spraying, are prepared in such a way as to obtain a stable fluid product that does not settle and they usually contain from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0 to 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as antifoams, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is little or not soluble: some organic solids or mineral salts may be dissolved in the support to help prevent sedimentation or as antifreezes for water.

 Wettable powders (or spray powder) are usually prepared to contain 20 to 95% active material, and usually contain, in addition to the solid carrier, from 0 to 5% wetting agent, to 10% of a dispersing agent, and, when necessary, from 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents, etc ...

For example, here are various compositions of wettable powders
Example F 3: active ingredient 50% - calcium lignosulfonate (deflocculant) 5% - isopropylnaphthalene sulfonate (agent
anionic wetting agent) 1% - Anti-caking silica 5% - Kaolin (charge) 39 X
Another 70% powder composition uses the following components:
Example F 4 :: - active ingredient 700 g - sodium dibutylnaphthylsulfonate 50 g - condensation product in proportions
3/2/1 naphthalene sulphonic acid,
of phenolsulfonic acid and
formaldehyde 30 g - kaolin 100 g - chalk of champagne 120 g
Another composition of 40% spraying powder uses the following constituents
Example F 5 - active ingredient 400 g - sodium lignosulfonate 50 g - sodium dibutylnaphthalene sulfonate 10 g - silica 540 g
Another composition of 25% spraying powder uses the following constituents:
Example F 6 :: - active ingredient 250 g - calcium lignosulfonate 45 g - equiponderal mixture of chalk of Champagne
and hydroxyethylcellulose 19 g - sodium dibutylnaphthalene sulfonate 15 g - silica 195 g - Champagne chalk 195 g - kaolin 281 g
Another 25 X powder composition uses the following constituents
Example F 7 - Active Ingredient 250 g - isooctylphenoxypolyoxyethylene ethanol 25 g - equiponderal mixture of chalk
Champagne and hydroxyethylcellulose 17 g - sodium aluminosilicate 543 g - kieselguhr 165 g
Another composition of 10% spraying powder uses the following constituents
Example F 8 - active ingredient 100 g - mixture of sodium salts of sulphates
of saturated fatty acids 30 g - condensation product of naphtha acid
sulfonic acid and formaldehyde 50 g - kaolin 820 g
In order to obtain these sprayable powders or wettable powders, the active ingredients are intimately mixed in appropriate mixers with the additional substances and milled with suitable mills or other mills. Spray powders are thus obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very advantageously especially for application to the leaves of plants.

 In place of the wettable powders, pasta can be made. The conditions and methods of production and use of these pastes are similar to those of wettable powders or powders to be sprayed.

 As already mentioned, the 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 may be of the water-in-oil or oil-in-water type and may have a thick consistency such as that of a "mayonnaise".

 The granules intended to be placed on the ground are usually prepared so that they have dimensions of between 0.1 and 2 mm and they can be manufactured by agglomeration or impregnation. In general, the granules contain 0.5 to 25% of active material and 0 to 10% of additives such as stabilizers, slow release modifiers, binders and solvents.

According to an example of granule composition, the following constituents are used:
Example F 9 - active ingredient 50 g - epichlorohydrin 2.5 g - cetyl polyglycol ether 2.5 g - polyethylene glycol 35 g - kaolin (particle size: 0.3 to 0.8 mm) 910 g.

 In this particular case, the active ingredient is mixed with epichlorohydrin and dissolved with 60 g of acetone; polyethylene glycol and cetyl polyglycol ether are then added. The kaolin is sprinkled with the resulting solution and the acetone is then evaporated under vacuum. Such a microgranule is advantageously used for controlling soil fungi.

 The compounds of formula (I) and the combinations can still be used in the form of dusting powders; a composition comprising 50 g of active material and 950 g of talc can also be used; a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc can also be used; these constituents are mixed and milled and the mixture is applied by dusting.

 The following nonlimiting examples illustrate the invention and show how it can be implemented.

 Examples 1 to 3 illustrate particular modes of preparation of compounds according to the invention, as well as these compounds themselves. Among the physical properties indicated for these compounds, the proton NMR displacement (delta) values of the -O-CH-O- (acetal) group were indicated. These displacements are measured in ppm and are marked against a reference product which is tetramethyl silane. NMR is carried out at 100 MHz in deuterated chloroform.

 Examples 4 to 10 illustrate the fungicidal properties of the compounds according to the invention as well as their applications.

Example 1
A product of formula is prepared

According to a process described in European Patent Application No. 151084, 40 ml of trifluoroethanol are mixed with 10.7 g of product of formula (V). HCl gas was bubbled so as to have a weight increase of 1.39 g. It is heated for 2 hours at 700C. It is poured into 500 ml of water containing 10 g of Na 2 CO 3. It is extracted with ethyl acetate; the organic solution is washed with water, dried, filtered and evaporated. 8 g of crystals consisting of a mixture of 2 diastereoisomers of the product of formula (I), melting from 800 and presenting with
NMR delta proton displacement at 5.18 and 5.41 ppm
Example 2
The product obtained in Example 1 is treated by liquid chromatography on a silica column under pressure of 0.3 bar (above atmospheric pressure) with an eluent consisting of a mixture of ethyl acetate / heptane in volume proportions. / 20.

 3 g of a first fraction A and 3.6 g of a second fraction B are collected.

 Each of these fractions gives a precipitate which crystallizes. Crystals A from fraction A correspond to one of the diastereoisomers. They melt at 840C and have delta proton displacement in NMR at 5.41 ppm. The diastereoisomer A is characterized in that the triazolylmethyl group and the trifluoroethoxy group are located on the same side of the tetrahydrofuran ring plane.

 The crystals B from fraction B correspond to the other diastereoisomer. they melt at 1670C and have delta proton displacement in NMR at 5.18 ppm.

préparé comme indiqué dans la demande de brevet européen ne151084. Example 3
40 ml of trifluoroethanol are mixed with 10.8 g of product of formula

prepared as indicated in European Patent Application No. 151084.

 HCl gas is bubbled to a weight increase of 1.5 g. It is heated for 4 hours at 700 ° C., poured into 500 ml of water containing 10 g of Na 2 CO 3. It is extracted using CHOC13; the organic phase is washed with water, dried, evaporated. 12.7 g of product of formula (I) are obtained in the form of a mixture of the two diastereoisomers.

Example 4
Four plots of land each bearing 4 apple trees of the variety known as "Calville" have been treated, which is very susceptible to scab (a disease whose Latin name is Venturia inaequalis and the English name is scab). The treatments took place every 12 days from flowering to the middle stage of fruit enlargement. These treatments consisted in applying a slurry, that is to say a dilute aqueous emulsion of the active ingredient described in Example 1. This slurry was applied at a rate of 10 hl / ha and was obtained by dilution of an emulsifiable concentrate. ; this concentrate itself contained 62 g / l of active material, 203 g / l of cyclohexanone, 609 g / l of acetophenone, 50 g / l of calcium alkylarylsulphonate, 100 g / l of polyethoxylated castor oil; the concentration of the slurry of active material was 2.5 g / hl.

 The results were compared with the nearest product of known closest chemical formula, that is, the formula of the compound of Example 42 of European Patent Application 151084; this product is hereinafter referred to as the reference product. The product thus used for the comparison included, as well as the product of Example 1 according to the invention, all the possible diastereoisomeric forms.

 The results were measured in the following manner phytotoxicity: measured one day after the third treatment and expressed as a percentage according to a visual assessment of the general state of the leaves and fruits; the value of 15% is the maximum acceptable value, leaf activity: measured one day after the 5th treatment and expressed as a percentage of the number of leaves with scab, fruit activity: measured at the end of treatment and expressed as a percentage of the number of fruits achieved.

The results were as follows:

<tb> I <SEP> I <SEP> phytotoxicity <SEP> activity <SEP> I <SEP> activity <SEP> I
<tb> I <SEP> I <SEP> I <SEP> leaves <SEP> I <SEP> fruits <SEP> I <SEP>
<tb> Iproduct <SEP> I <SEP> I
<tb> Ide <SEP> the ex.ll <SEP> 1 <SEP> 1 <SEP> 32.2 <SEP> 1 <SEP> 4,4 <SEP> 1
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> Iproduct <SEP> I <SEP> I <SEP> I
<tb> Ide <SEP> refer to <SEP> I <SEP> 1 <SEP> 1 <SEP> 80.0 <SEP> 1 <SEP> 58.7 <SEP> 1
<tb> I <SEP> rence <SEP> I <SEP> I <SEP> I
<tb> Itemoin <SEP> I <SEP> l <SEP> I <SEP> I
<tb> I <SEP> no <SEP> j <SEP> o <SEP> 1 <SEP> 99.8 <SEP> 1 <SEP> 84.2 <SEP> l <SEP>
<tb> Itraité <SEP> I <SEP> I <SEP> I
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Example 5
The procedure is as in Example 4, but treating apple trees of the Golden variety with a slurry having a concentration of active ingredient of 5 g / hl.

The results are as follows

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<tb> leaves <SEP> fruits
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<tb> product
<tb><SEP> 39.8 <SEP> 5.9
<tb> references
<tb> Itemoin <SEP> I <SEP> I <SEP> I
<tb> I <SEP> no <SEP> I <SEP> O <SEP> 1 <SEP> 99.7 <SEP> 1 <SEP> 87 <SEP> 1
<tb> Itressed <SEP> I <SEP> l <SEP> l <SEP> I <SEP>
<Tb>
Example 6
Four plots of land each bearing 15 vines of the variety known as
Carignan, which is very sensitive to powdery mildew (a disease whose Latin name is Uncinula necator and the English name is powdery mildew). Treatments took place every 14 days from the bursting of the buds to the veraison (period of change colored bunches of grapes)
These treatments consisted in applying a slurry of the same nature as in Example 4 at a rate of 1.5 g / hl.

The results, obtained and compared as in Example 4, were as follows

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<tb> I <SEP> (measured <SEP> 13 <SEP> j <SEP> I (measured <SEP> 8 <SEP> j <SEP> aftereffects (measured <SEP>
<tb> í <SEP> after <SEP> on <SEP> 2nd <SEP> I <SEP> on <SEP> 3rd <SEP> 114 <SEP> j <SEP> after <SEP> on <SEP> I
<tb> I <SEP> I <SEP> treatment) <SEP> i <SEP> treatment) <SEP> I <SEP> treatment) <SEP> I <SEP>
<tb> Iproduct <SEP> í <SEP> I <SEP> I
####
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP>
<tb> Iproduct <SEP> I <SEP> I
<tb> I <SEP> of <SEP> I <SEP> O <SEP> I <SEP> 29.5 <SEP> 1 <SEP> 0 <SEP> l <SEP>
<tb> Ireferencel <SEP> I <SEP> I <SEP> I <SEP>
<tb> Itemoin <SEP> I <SEP> I
<tb> I <SEP> no <SEP> I <SEP> O <SEP> I <SEP> 100 <SEP> 1 <SEP> 96.2 <SEP> l <SEP>
<tb> I <SEP> treated <SEP> I <SEP> I <SEP> I
<Tb>
Example 7-10
Four plots of land of 10 m2 with a wheat crop were treated. One or two treatments were performed when the first symptoms of disease appeared in the fields.

 The treatment slurry was of the same kind as in Example 4 and was applied in an amount such that the dose of active ingredient was 90, 120 or 150 g / ha according to the tests.

 In all trials, no phytotoxicity was observed.

 In Example 7, a wheat culture of the Nebraska variety with yellow rust (Puccinia striiformis) was treated, the results being observed, 10 days after the 2nd treatment, on the highest leaf just below the ear.

 In Example 8, a wheat crop of the Vaillant variety suffering from brown rust (Puccinia recondita) was treated, the results being observed, 19 days after the first treatment, on the highest leaf just below the ear.

 In Example 9, a wheat cultivation of the Longbow variety affected with septoria (Septoria tritici) was treated, the results being observed, 46 days after the single treatment, on the highest leaf just below the spike. .

 In Example 10, a wheat crop of the Roazon variety was treated, the results being observed 44 days after the single treatment on the th sheet from the ear (the first or highest leaf being free from disease). This late measure illustrates the good persistence of the products.

The results were measured and expressed as: leaf activity: percentage of the number of leaves affected by the disease leaf area activity: percentage of leaf area affected by the disease
The results were as follows:

<tb> I <SEP> I <SEP> dose <SEP> example <SEP> 7 <SEP> 1 <SEP> example <SEP> 8
<tb> I <SEP> I <SEP> in <SEP> I <SEP> activity <SEP> I <SEP> activity <SEP> I <SEP> activity <SEP> I
<tb> g / ha <SEP> sheet <SEP> sheet <SEP> surface <SEP> of
<tb> sheet <SEP>
<tb> I <SEP> Product <SEP> 1 <SEP> 90 <SEP> 1 <SEP> 4.6 <SEP> 1 <SEP> 75 <SEP> 1 <SEP> 2.8 <SEP> I <SEP >
<tb> Ide <SEP> the ex.ll <SEP> 120 <SEP> 1 <SEP> 2.1 <SEP> 1 <SEP> 36 <SEP> 1 <SEP> 0.8 <SEP> I <SEP >
<tb> I <SEP> I <SEP> 150 <SEP> 1 <SEP> 1,2 <SEP> 1 <SEP> 28 <SEP> 1 <SEP> 0.6 <SEP> i <SEP>
<tb> product <SEP>
<tb> Ide <SEP> ref <SEP> I <SEP> 90 <SEP> i <SEP> 39.2 <SEP> 1 <SEP> 88 <SEP> 1 <SEP> 8.8 <SEP>
<tb> I <SEP><SEP> 1 <SEP> 120 <SEP> 1 <SEP> 27.3 <SEP> 1 <SEP> 93 <SEP> 1 <SEP> 5.4 <SEP>
<tb> 150 <SEP> 19.5 <SEP> 74 <SEP><SEP> 4.7 <SEP>
<tb> witness
<tb><SEP> no <SEP> 0 <SEP> 80 <SEP> 100 <SEP> 27.2
<tb> I <SEP> treated <SEP> I <SEP> I <SEP> I
<tb><SEP> I <SEP> I <SEP> dose <SEP> I <SEP> example <SEP> 9 <SEP> 1 <SEP> example <SEP> 10 <SEP> 1
<tb><SEP> I <SEP> I <SEP> in <SEP> I <SEP> activity <SEP> I <SEP> activity
<tb> I <SEP> I <SEP> g / ha <SEP> I <SEP> surface <SEP> of <SEP> I <SEP> surface <SEP> of <SEP> I
<tb> I <SEP> I <SEP> I <SEP> sheet <SEP> I <SEP> sheet <SEP>
<tb> I <SEP> Product <SEP> 1 <SEP> 90 <SEP> 1 <SEP> 3.6 <SEP> 1 <SEP> 21.6 <SEP><SEP> 1 <SEP>
<tb> Ide <SEP> the ex.l <SEP> i <SEP> 120 <SEP> 1 <SEP> 2,6 <SEP> 1 <SEP> 10,3 <SEP> 1
<tb> I <SEP> 1 <SEP> 150 <SEP> 1 <SEP> 2.9 <SEP> 1 <SEP> 3.9
<tb> Product <SEP> I <SEP>
<tb> Ide <SEP> ref- <SEP> 1 <SEP> 90 <SEP> 1 <SEP> 6.9 <SEP> 1 <SEP> 10.9 <SEP>
<tb> I <SEP><SEP> 1 <SEP> 120 <SEP> 1 <SEP> 7.7 <SEP> i <SEP> 11.7 <SEP>
<tb> 1 <SEP> 150 <SEP> 1 <SEP> 4,8 <SEP> ~ <SEP> ~ <SEP>! <SEP> 15.9
<tb> witness <SEP>
<tb> no <SEP> 0 <SEP> 21.4 <SEP> 1 <SEP> 58.7
<tb> processed
<Tb>
Example 11
In vivo test on Erysiphe graminis f.sp.hordei on barley (barley powdery mildew)
An aqueous emulsion of the active ingredient to be tested having the following composition is prepared by fine grinding:
- active ingredient to be tested 90 mg
- Tween 80 (surfactant constituted
of a polyoxyethylenated derivative oleate of the
sorbitan) diluted to 10% in the 0.45 ml vise
- water 90 mi.

 This aqueous emulsion is then diluted with water to obtain the desired concentration.

 Barley, sown in loam, is treated at the stage 10 cm high by spraying an aqueous emulsion (called slurry) concentration indicated below. The test is repeated twice. After 24 hours, the barley plants are dusted with Erysiphe graminis spores, the dusting being done with diseased plants.

 The reading is done 8 to 12 days after the contamination.

Under these conditions, the following results are observed:
At a dose of 0.1 g / l, total protection (greater than or equal to 95%) with the compounds of Example 1 and the compound
A of example 2.

Example 12
In vivo test on "Puccinia recondita" responsible for wheat rust
Wheat, in buckets, sown in loam, is treated at the stage 10 cm high by spraying with aqueous emulsions (called boiled) of the same composition as that described in Example II and at various concentrations of the test compound. . The test is repeated twice with each concentration.

 After 24 hours, an aqueous suspension of spores (50000 sp / cm3) is sprayed on the wheat; this suspension was obtained from contaminated plants. The wheat is then placed for 48 hours in an incubation cell at about 180 ° C and 100% relative humidity.

 After 2 days, the relative humidity is reduced to 60%. The control of the condition of the plants is between the 11th and 15th day after the contamination compared to the untreated control.

Under these conditions, the following results can be observed:
At a dose of 0.1 g / l, total protection with the compounds of Examples 1 and 2 (compound A).

Example 13
In vitro tests on seed fungi and soil fungi
The action of the compounds according to the invention on the following fungi responsible for secondary diseases of cereals is studied:
Pseudocercosporella herpotrichoides (CERC)
Helminthosporium gramineum (HELM G)
Botrytis cinerea (BOT)
Pyrenophorae avenae (PYRE)
Septoria nodorum (SEP N)
Helminthosporium teres (HELM T)
The indications in parentheses will be used to represent these fungi in Table (II).

 For each test, the procedure is as follows: a nutrient medium consisting of potato, glucose and gelose (PDA medium) is supercooled in a series of Petri dishes (20 ml per box) after sterilization with autoclave at 1200C.

 During the filling of the canisters, an acetonic solution of the active material is injected into the supercooled medium in order to obtain the desired final concentration.

 Petri dishes analogous to the preceding ones, in which similar amounts of a nutrient medium containing no active material are cast as a control.

 After 24 or 48 hours each box is seeded by depositing a fragment of mycelium from a previous culture of the same fungus.

 The boxes are stored for 2 to 10 days (depending on the fungus tested) at 220C and then comparing the growth of the fungus in the boxes containing the active ingredient to be tested, that of the same fungus in the boot used as a control.

 For each test compound, the lowest dose is thus determined, making it possible to inhibit the development of the fungus under consideration at 80-100%. This dose is called "Minimal inhibitory concentration".

These minimum inhibitory concentrations, expressed in ppm, are reported in the following table, in which the abbreviations have the meaning indicated above.

<Tb>

I <SEP> COMPOUND <SEP> I <SEP> Minimum <SEP> Minimum <SEP> Inhibitory <SEP> In <SEP> mg / i <SEP> I <SEP>
<tb> I <SEP> I <SEP> CERC <SEP> I <SEP> HELM <SEP> G <SEP> I <SEP> HELM <SEP> T <SEP> I <SEP> PYRE <SEP> I <SEP > SEPT <SEP> N <SEP> I <SEP> BOT <SEP> I
<tb> I <SEP> 1 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1 <SEP> 2 <SEP> (A) <SEP> 10 <SEP> I <SEP> 30 <SEP> I <SEP> 10 <SEP> l <SEP> 100 <SEP> 1 <SEP><SEP> 1 <SEP> 30 <SEP> 1
<tb> I <SEP> 1 <SEP> I <SEP> 3 <SEP> l <SEP> 100 <SEP> l <SEP> 10 <SEP> l <SEP> 10 <SEP> 1 <SEP> 30 <SEP > 1 <SEP> 30 <SEP> 1
<tb> I <SEP> I <SEP><SEP> t <SEP> I <SEP> t <SEP> I <SEP> I <SEP> I <SEP>
<Tb>
The concentrations of suspensions of active ingredient used in the preceding examples were indicated in g / l and correspond substantially to application rates provided with the same figures but expressed in g / ha.

The following examples illustrate the
properties of the associations according to the invention.

EXAMPLE 14 In Vitro Test on Septoria nodorum (iprodione compound)
In a series of sterile Petri dishes, a nutrient medium is introduced supercooled.

 During filling, an acetonic solution of the active ingredient consisting of the combination of the compound obtained according to Example IV with iprodione is injected into the supercooled medium in various proportions in order to obtain the desired concentration of active ingredient.

 Petri dishes similar to the preceding ones filled as indicated above are used as controls, except that the nutrient medium contains no active ingredient.

 After 24 hours, each box is seeded by depositing a fragment of mycelium from a previous culture of the same fungus.

 The boxes are stored for 15 days at 2200C - + 2 and the growth of the fungus is compared in the dishes containing the active ingredient (s) to be tested, to that of the same fungus in the control boxes.

Under these conditions, the percentage inhibition is calculated according to the following formula
I = T - TT x 100
Td in which
I is the percentage of inhibition,
T is the average diameter, in mm, of the mycelial development in the control box,
TT is the average diameter, in mm, of the mycelial development in the treated box, and d is the diameter of the mycelial fragment deposited at the beginning of the test.

 Under these conditions, the results recorded below are obtained in the form of the percentages of real inhibition Ir.

X inhibition on Septoria nodorum

<tb> I <SEP> IPRODIONE <SEP> I <SEP> Compound
<tb> IDose <SEP> of <SEP> matter <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> 0 <SEP> i <SEP> 0.3 <SEP> 1 <SEP> 3 <SEP> l <SEP>
<tb> 0 <SEP> 0 <SEP> 43 <SEP> 69
<tb> I <SEP> 3 <SEP> 1 <SEP> 70 <SEP> 1 <SEP> 85 <SEP> 1 <SEP> 95 <SEP> 1
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP>
<tb> I <SEP> 10 <SEP> I <SEP> 83 <SEP> 1 <SEP> 90 <SEP> l <SEP> 100 <SEP> 1
<Tb>
Example 15 - In vitro test on Septoria nodorum (compound / fenpropimorph) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> FENPROPIMORPH <SEP> I <SEP> Compound <SEP> I <SEP>
<tb> IDose <SEP> of <SEP> matter <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> 1 <SEP> 1 <SEP> I <SEP> ~ <SEP> 3 <SEP> 1
<tb> 0 <SEP> 0 <SEP> 62 <SEP> 69
<tb> 1 <SEP> 76 <SEP> 90 <SEP> 94 <SEP>
<tb> 2 <SEP> 83 <SEP> 93 <SEP> 98 <SEP>
<Tb>
Example 16 - In vitro test on Septoria nodorum (compound / tridemorphe) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> TRIDEMORPH <SEP> I <SEP> Compound
<tb><SEP> Dose <SEP> of <SEP> matter <SEP> I
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> 1 <SEP> 0.3 <SEP> l <SEP> 1 <SEP> i <SEP>
<tb> 0 <SEP> 43 <SEP> 1 <SEP> 62
<tb> 0.3 <SEP> 72 <SEP> 82 <SEP> 90
<tb> 1 <SEP> 90 <SEP> 95 <SEP> 96
<Tb>
Example 17 - In vitro test on Septoria tritici (compound / captafol) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> CAPTAFOL <SEP> I <SEP> Compound
<tb> IDose <SEP> of <SEP> matter
<tb> lactive <SEP> in <SEP> mg / l <SEP> 0 <SEP> 3
<tb> 0 <SEP> 0 <SEP> 35
<tb> 100 <SEP> 84 <SEP> 92
<tb> 300 <SEP> 100 <SEP> 100
<Tb>
Example 18 - In vitro test on Botrytis cinerea (compound / carbendazim) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> CARBENDAZIME <SEP> I <SEP> Compound <SEP> I
<tb> Dose <SEP> of <SEP> matter <SEP> I <SEP> I <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> 1 <SEP> 10
<tb><SEP> i <SEP> I- <SEP>
<tb> I <SEP> o <SEP> I <SEP> o <SEP> I <SEP> 35 <SEP> 1
<tb> I <SEP> 0.08 <SEP> 1 <SEP> 72 <SEP> 1 <SEP> 85 <SEP> I <SEP>
<Tb>
Example 19 - In vitro test on Botrytis cinerea (compound / captan) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> CAPTANE <SEP> I <SEP> Compound <SEP> l <SEP>
<tb> IDose <SEP> of <SEP> matter <SEP> I
<tb> lactive <SEP> in <SEP> mg / l <SEP> 0 <SEP> 10
<tb> 0 <SEP> 0 <SEP> 35
<tb> I <SEP> lo <SEP> 1 <SEP> 9 <SEP> 1 <SEP> 86 <SEP> 1
<Tb>
Example 20 - In vitro test on Botrytis cinerea VE 35 (compound / iprodione (= resistant to iprodione and carbendazim) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> IPRODIONE <SEP> I <SEP> Compound <SEP> I
<tb> IDose <SEP> of <SEP> matter <SEP> I <SEP><SEP> i <SEP> I <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> i <SEP> 10 <SEP> I
<tb> I <SEP> i <SEP> I <SEP> I
<tb> t <SEP> O <SEP> t <SEP> O <SEP> 0 <SEP> 88 <SEP> i <SEP>
<tb> 3 <SEP> 90 <SEP>
<Tb>
Example 21 - In vitro test on Alternaria tenuis (compound / iprodione) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> IPRODIONE <SEP> | <SEP> Compound
<tb> IDose <SEP> of <SEP> matter <SEP> l <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> 0 <SEP> I <SEP> 10 <SEP> I
<tb> 0 <SEP> 0 <SEP> 68
<tb> 10 <SEP> 1 <SEP> 90 <SEP> l <SEP> 100 <SEP>
<Tb>
Example 22 - In vitro test on Monilia lasca (compound / carbendazim) same operating conditions as in the previous example.

The results are recorded below

<tb><SEP> I <SEP> CARBENDAZIME <SEP> I <SEP> Compound
<tb> IDose <SEP> of <SEP> material <SEP> I <SEP> I
<tb><SEP> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> I <SEP> 0.3 <SEP> I <SEP> 1 <SEP> I
<tb><SEP> i <SEP> i <SEP> i <SEP>
<tb><SEP> I <SEP> O <SEP> I <SEP> O <SEP> 31 <SEP> 1 <SEP> 77 <SEP> 1
<tb> 1 <SEP> 0.008 <SEP> 1 <SEP> 76 <SEP> 1 <SEP> 86 <SEP> l <SEP> 100 <SEP> I
<tb> 0.015 <SEP> 92 <SEP> 92 <SEP> 95 <SEP>
<Tb>
Example 23 - In vitro test on Helminthosporum gramimeum (compound / fenpropimorph) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> FENPROPIMORPHE <SEP> I <SEP> Compound <SEP> t <SEP>
<tb><SEP> Dose <SEP> of <SEP> matter <SEP> I <SEP> l <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> I <SEP> 10 <SEP> 1 <SEP> 30 <SEP> I
<tb> 0 <SEP> 0 <SEP> 65 <SEP> 75 <SEP> 1
<tb> 0.1 <SEP> 0.00 <SEP> 78 <SEP> 69 <SEP>
<tb> I <SEP> 0.3 <SEP> 1 <SEP> 0.00 <SEP> 1 <SEP> 52 <SEP> 1 <SEP> 75 <SEP> i <SEP>
<Tb>
Example 24 - In vitro test on Fusarium roseum (compound / chlorotalonil) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> CHLOROTALONIL <SEP> I <SEP> Compound
<tb> Dose <SEP> of <SEP> matter <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> 1 <SEP> 0.3 <SEP> 1 <SEP> 30 <SEP> 1
<tb> 0 <SEP> 0 <SEP> 56 <SEP> 49
<tb> I <SEP> 100 <SEP> 1 <SEP> 51 <SEP> 1 <SEP> 51 <SEP> i <SEP> 75 <SEP> i <SEP>
<tb> i <SEP> I <SEP> I <SEP> i <SEP> I <SEP>
<tb> 300 <SEP> 73 <SEP> 74 <SEP> 83
<Tb>
Example 25 - In vitro test on Fusarium roseum (compound / manebe) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> MANEBE <SEP> I <SEP> Compound
<tb> IDose <SEP> of <SEP> matter <SEP> I
<tb> lactive <SEP> in <SEP> mg / l <SEP> I <SEP> O <SEP> 1 <SEP> 0.3 <SEP> 1 <SEP> 30 <SEP> I <SEP>
<tb> 0 <SEP> 0 <SEP> 6 <SEP> 49
<tb> 30 <SEP> 75 <SEP> 83 <SEP> 85
<tb> i <SEP> 50 <SEP> 1 <SEP> 73 <SEP> 1 <SEP> 78 <SEP> 1 <SEP> 83 <SEP> I
<Tb>
Example 26 - In vitro test on Venturia pirina (compound / captan) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> CAPTANE <SEP> | <SEP> Compound
<tb> IDose <SEP> of <SEP> matter <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> 0 <SEP> 10 <SEP> 100
<tb> 0 <SEP> 0 <SEP> 70 <SEP> 94
<tb> 30 <SEP> 46 <SEP> 78 <SEP> 95 <SEP>
<tb> 100 <SEP> 62 <SEP> 88 <SEP> 95 <SEP>
<Tb>
Example 27 - In vitro test on Pseudocercosporella herpotrichoides (compound / tridemorphe) same operating conditions as in the previous example.

The results are recorded below

<tb> I <SEP> TRIDEMORPH <SEP> I <SEP> Compound
<tb><SEP> Dose <SEP> of <SEP> matter <SEP> I <SEP> l <SEP>
<tb> lactive <SEP> in <SEP> mg / l <SEP> 1 <SEP> 0 <SEP> 1 <SEP> 0.3 <SEP> 1 <SEP> 3
<tb> 0 <SEP> 0 <SEP> 22 <SEP> 1 <SEP> 77
<tb> t <SEP> 0.3 <SEP> 1 <SEP> 18 <SEP> 1 <SEP> 41 <SEP> 1 <SEP> 80
<tb> I <SEP> I <SEP> I <SEP> I <SEP>
<tb> I <SEP> 1 <SEP> I <SEP> 52 <SEP> 1 <SEP> 64 <SEP> 1 <SEP> 91
<tb> i <SEP> i <SEP>
<tb> 3 <SEP> 3 <SEP> i <SEP> 86 <SEP> 1 <SEP> ~ <SEP><SEP> 86 <SEP> 1 <SEP> 96
<Tb>
Example 28 - In vitro test on Erysiphe graminis special form hordei on barley (barley powdery mildew)
One operates in the same way as for Example 11 with as active ingredient a combination of the compound obtained according to Example IV with the tridemorph in a 1: 1 weight ratio.

 At a dose of 0.06 g / l protection, total (greater than 95%).

Example 29 - In vivo test on Botrytis cinerea on tomato
An aqueous emulsion is prepared in the same manner as that indicated in Example 11, using as active ingredient a combination consisting of the compound obtained according to Example IV and Iprodione in a weight ratio equal to 1.

 Tomatoes grown in greenhouse (variety Marmande) aged 30 to 40 days are sprayed with the aqueous emulsion.

 After 24 or 48 hours, the leaves are cut and placed in 2 petri dishes (diameter 11 cm), the bottom of which has been previously filled with a wet filter paper disk (5 leaflets per box).

The inoculum is then brought with the help of a syringe by depositing drops (3 drops per leaflet) of a suspension of spores. This suspension of spores
Botytris cinerea was obtained from a 15-day culture, then suspended in a nutrient solution (80,000 units / cm).

 The control is done 6 days after the contamination compared to a non-triaged control.

 At a dose of 0.1 g / l total protection (greater than or equal to 95%).

NOMENCLATURE TABLE
Chlorothalonil Tetrachloro-isophthalonitrile iprodione 3- (3,5-dichlorophenyl) -N-isopropyl-2,4-dioxo
imidazolidin-l-carboxamide
Fenpropimorph (t) -cis-4-C3- (4-tert-butylphenyl) -2-methylpropyl) -2,6-dimethylimorpholine
Tridemorph 2,6-dimethyl-4-tridecylmorpholine
Dinocap 2- (1-methylheptyl) -4,6-dinitrophenyl
crotonate
Dithianon 5,10-dihydro-5,10-dioxonaphthol (2,3-b 1-i, 4-dithia-anthraquinone
Manèbe Ethylene bis (dithiocarbamate) of manganese
Mancozeb Maneb complex with a zinc salt
Phosethyl-Al aluminum Tris-O-ethylphosphonate
Captan N- (trichloromethylthio) cyclohex-4-ene-1,2
dicarboximide
Carbendazime Methyl Benzimidazol-2-yl Carbamate
Captafol N- (1,1,2,2-tetrachloroethylthio)
cyclohex-4-ene-1,2-dicarboximide

Claims (13)

 as well as agriculturally acceptable salts of these products as claimed in claim 1) of the patent application No. 85.19194 and one or more compounds selected from the group (II) consisting of the following subclasses 1. The derivatives chlorinated or nitrated benzene such as quintozene or chlorothalonil, 2. Dicarboximide derivatives such as captan, foipel, captafol, iprodione, procymidone, 3. Derivatives comprising one or more heterocycles such as quinolines, morpholines, 4. Phosphorous acid derivatives such as metal phosphites, 5. Derivatives of dithiocarbamic acid such as manebe or mancozeb, 6. Phenol derivatives such as dinocap, 7. Quinone derivatives such as dithianon, 8. Carbamic acid derivatives and benzimidazoles such as carbendazim, benomyl, thiophanate-methyl,

 several formula products  characterized in that they consist of one or  CLAIMS 1) Associations that can be used especially as a fungicide,  9. Sulfur derivatives,  10. Amines and amides such as dichloran,  carboxin, triforine, cymoxanil, metalaxyl, lofurace,  11. Diazines such as chinomethionate,  fenarinol, anilazine,  12. Sulfonamides such as dichlofluanid,  13. Guanidines such as doguadine.  captan, carbendazim, captafol, sulfur.  dinocap, dithianon, maneb, mancozeb, phosethyl-Al,  chlorothalonil, iprodione, fenpropimorph, tridemorph,  following active ingredients  what the products of the group are chosen among the 2) Associations according to claim 1) characterized in  it is between 0.0003 and 3000.  of formula (I) with the active substance (s) of the group  characterized in that the weight ratio of the compound 3) Associations according to one of claims 1 or 2)  3000.  that the weight ratio is between 0.001 and 4) Associations according to claim 3) characterized in  claims 1 to 4) as a fungicide. 5) Use of associations according to one of the  inert, acceptable in agriculture.  one of claims 1 to 4) and at least one support  contains as active ingredient an association according to 6) Fungicidal composition characterized in that it  contains 0.5 to 95% of active ingredient. 7) Fungicidal composition characterized in that it  Claims 1 to 4).  effective association according to one of the  cultures, characterized in that a dose is applied 8) Method for controlling fungal diseases of  kg / ha, preferably from 0.01 to 0.5 kg / ha.  that the association is applied at the rate of 0.005 to 5 9) Method according to claim 8) characterized in that