FR2608898A1 - Fungicidal combinations based on cyanobenzimidazole and on a systemic fungicide - Google Patents

Abstract

The combination relates to a fungicidal product resulting from the combination of at least one compound of formula I: in which R'' represents a dialkylamino radical containing from two to four carbon atoms, with at least one compound of group II consisting of: a) phosphorous acid or its alkaline salts or the derivatives of phosphorous acid, b) acetamides, c) acylanilides.

Description

 The invention relates to new products resulting from new synergistic antifungal combinations of active ingredients, comprising on the one hand at least one 2-cyano-dialkyl sulfamoyl 4-bromo-6-trifluoromethylbenzimidazole derivative and on the other hand another active ingredient which will be defined below. It also relates to a process for the preparation of these products, the use of these products as a fungicide, fungicidal compositions based on these products and a method of treating plants with these products.

 It is known that diseases caused by oomycete fungi are particularly serious.

Among the large number of foliar diseases thus caused, we can mention the mildew of vines, tobacco, tomatoes, potatoes and cucurbits.

 EP-A-0087375 has already proposed novel 2-cyano benzimidazole derivatives which can be used in fungicidal compositions for agricultural use, especially as a contact fungicide and having a good efficacy against several types of downy mildew, especially the late blight of nightshade (eg tomato and potato), Phytophthora infestans, tobacco blight, Peronospora tabacina and Phytophtora parasitica, vine blight Plasmopara viticola, late blight of cucurbitaceae Pseudoperonospora cubersis.

 Nevertheless, it is desirable to always broaden the spectrum of activity and performance of a fungicide.

 It is known, moreover, to use the compounds of the families listed below against various plant fungal diseases, in particular the downy mildew of the vine and Solanaceae, as systemic fungicides phosphorous acid and its derivatives, acetamides , acylalanines, acylamino oxazolidinones.

 Phosetyl-Al, a common name for aluminum tris O-ethylphosphonate or aluminum ethyl phosphite, is used to protect vines and other plants against phycomycetes. This product has a remarkable action in preventive treatment and a curative activity secondary to its normal dose of use.

 Similarly, cymoxanil exhibits antifungal activity against the agents of the plants' downy mildews.

However, its activity is limited by its persistence of insufficient action.

 Metalaxyl is commonly used for various mildews in soil and leaf treatments. However, this product does not sufficiently control some resistant strains. Oxadixyl has a lower activity than metalaxyl but has been shown to be very useful in combination with other fungicides.

 It has now been observed that, surprisingly, the combination of at least one 2-cyano-benzimidazole derivative of formula (I) in which R is a dialkylamino radical having 2 to 4 carbon atoms with a group II fungicide ) consisting in particular of phosphorous acid or phosphorous acid derivatives such as metal alkylphosphites, acetamides, acylanilides such as acylalanines, butyrolactones acylamino, oxazolidinonesacylamino resulted with respect to certain fungi a synergistic effect resulting, for these associations, antifungal efficacy remarkably higher than what could have been expected from the antifungal properties of each component considered separately.

Note: Formulas are collected at the end of the description on special pages.

The active ingredients of group (II) are known active ingredients, most of them being described in detail in books such as "The
Pesticide Manual "edited by" The British Crop Protection
Council "whose 7th edition dates from 1983 or the" Farm
Chemical Handbook, 1986 Edition. The chemical names of the products listed are indicated on the last page of the description.

 It is certainly known to associate systemic fungicides of the type of those just mentioned with contact fungicides, but on the one hand the level of synergism observed is not very high and with often significant proportions of fungicide. contact and on the other hand it was not easy to select cyanobenzimidazoles unknown hitherto for the purpose of making associations.

 Thus, an object of the present invention is to provide combinations revealing a fungicidal synergy especially with respect to mildews.

 Another object of the present invention is to provide combinations revealing reduced toxicity.

 Another object of the present invention is to provide associations having excellent persistence.

 By "persistence of effectiveness" is meant the time during which the antifungal efficacy of an association continues to maintain a satisfactory level after antifungal treatment carried out on a culture by means of this combination.

The invention therefore relates first of all to a product resulting from the combination of at least one compound of group (I) formed by the compounds of formula (I) defined above with at least one compound of group (II) constituted by (a) phosphorous acid or its alkaline salts or derivatives
phosphorous acid preferably the derivatives of
formula (II) in which
R 'is a hydrogen or alkali metal atom or a
alkyl radical containing from 1 to 4 carbon atoms
carbon;
M is a hydrogen atom or an atom of a metal
alkaline, alkaline earth or aluminum
n 'is an integer of 1 to 3 equal to valence M.

Preferably, when R 'is a hydrogen atom or
alkali metal, M is an alkali metal and n '= 1.

Preferably, the derivative is an alkyl phosphite
metal, preferably phosetyl-Al or a derivative
alkaline phosphorous acid or phosphorous acid
himself.

b) acetamides, such as those described in US Pat.
No. 3,957,847, the contents of which are incorporated by reference
and preferably having the formula (III) in
which: R1, R2 identical or different
represent a C1 to C13 alkyl group of
preferably C1 to C4 and preferably cymoxanil
(R1 = CH3, R2 = c2H5).

c) Acylanilides such as those described in the patents
number 827 671 and 827 419 or European No 0026873 with
the content is incorporated pr reference and preferably
1) those of formula (IV) in which
R3, R4 identical or different represent a
hydrogen atom or an alkyl group of C1 to
C4, preferably methyl, or alkoxy from C1 to
C4, advantageously R3 - R4 - methyl.

R5 represents a group -CH2-R6 in which R6
is an alkoxy group of C1 to C4,
preferably methoxy, or aryl, preferably phenyl,
a halogen atom, preferably chlorine, or
R5 represents a C3 to C6 cycloalkyl of
cyclopropane, or a heterocycle
C5 or C6, preferably C5, having one or
two heteroatoms, preferably 2-furyl, the
5-isoxazolyl, 3-oxazolyl.

R7 is a hydrogen atom, a halogen atom or a radical
C2-C4 alkyl, preferably methyl
and advantageously, metalaxyl, furalaxyl,
benalaxyl, the compound where R3-R4-CH3, R7 = H,
R5-5-isosazolyl (LAB 149 202 F).

2) or those of formula (V) in which
R3, R4, R5, R6, R7 have the same meaning
only for formula (IV) with the same variants
preferred and R8 is a 3-oxazolidinonyl ring or
3-butyrolactonyl or 3-thiobutyrolactonyl or
3-thiooxazolidinonyl, advantageously oxadixyl,
cyprofuram, ofurace, CGA 68099 (RE 26745) in
where R3 = R4 - methyl, R7 = H, R5 =
-CH2OCH3, R8 = 3-butyrolactonyl, RE 26940 where
R3 = R4 = CH3, R7 = H, R5 = CH2OCH3,
R8 = 3-thiobutyrolactonyl, M12279 or R3 = R4 =
CH3, R5 = -CH2OCH3, R7 = 3-Cl, R8
3-oxazolidinonyl.

Some of these compounds are described in the patent
No. 884 661, the contents of which are incorporated by
reference. The compounds of formula (I) are described in
the unpublished French patent application filed on the 19th
February 1986 under registration number 8602455.

 The preparation of the compounds of formula (I) consists of reacting the 2-cyano-4-bromo-6-trifluoromethylbenzimidazole of formula (VI) or one of its salts, advantageously an alkali metal or alkaline earth metal salt, or ammonium salt, optionally substituted, with the halide of formula (VII) X-SO 2 -R "in which X represents a halogen atom (preferably a chlorine atom) and R" has the same meaning as in formula (I).

 The reaction of the compound (VI) with the halide (VII) is advantageously carried out in the presence of an acid acceptor, in an anhydrous or non-anhydrous medium, in a solvent, which is inert under the reaction conditions, generally at room temperature. boiling temperature of the solvent. As acid acceptors, mention may be made of mineral bases such as, for example, sodium hydroxide or potassium hydroxide, alkali metal or alkaline earth metal carbonates, nitrogenous bases such as triethylamine. Preferred solvents are aprotic polar solvents, such as, for example, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, methyl ethyl ketone, acetonitrile, N-methylpyrrolidone, ethyl acetate.

If desired, this reaction may be carried out in the presence of a suitable catalyst. As a useful catalyst, there may be mentioned phase transfer catalysts, such as, for example, quaternary ammonium salts.

 The reaction of the (optionally substituted alkali metal, or alkaline earth metal, or ammonium salt) of the compound (VI) with the halide (VII) does not require the presence of an acid acceptor. It is carried out in an anhydrous or non-anhydrous medium, in a solvent which is inert under the reaction conditions, generally at the boiling point of the solvent. The polar aprotic solvents mentioned above can be used advantageously in this reaction.

 If desired, this reaction can be carried out in the presence of a suitable catalyst, such as, for example, a phase transfer catalyst (for example a quaternary ammonium derivative).

 The optionally substituted alkali metal, or alkaline-earth metal or ammonium salt of the compound (VI) is prepared in a preliminary operation, optionally carried out in situ, by the action of a suitable base (for example sodium hydroxide, potassium hydroxide, ammonia, baryte, lime, etc.) or an alkali metal carbonate, or an alkali metal alcoholate (for example sodium methoxide or sodium or potassium ethylate) on this compound (VI).

 At the end of the reaction, whatever the process used, the compound formed is isolated from the reaction medium by any means known per se, such as, for example, by distillation of the solvent, or by crystallization of the product in the reaction medium, or by filtration, and then if necessary, this compound is purified by usual methods such as recrystallization in a suitable solvent.

 2-cyano-4-bromo-4-trifluoromethylbenzimidazole, of formula CVI) can be prepared by the action of ammonia on trichloromethyl-2-bromo-4-trifluoromethyl-6-benzimidazole, of formula (VIII) according to the method described in the application European Patent No. 87,375 Method A) and US Pat. No. 3,576,818. To carry out this operation the compound (VIII) is advantageously dissolved in a solvent such as dimethylformamide, 1,2-dimethoxyethane, acetonitrile, ethyl acetate or ethyl alcohol, this list being non-limiting. It can also be prepared according to either of the methods B and C described in European Patent Application No. 87,375.

 If desired, the preparation of the compound of formula (VI) from the compound of formula (VIII) can be carried out successively in a same reactor, then the conversion of the compound of formula (VI) into a compound of formula (I)> without isolating the intermediate compound formed (compound of formula (VI) or salt thereof).

 The compound of formula (VIII) may be prepared by the action of methyl trichloroacetimidate on 1,2-diamino-3-bromo trifluoromethyl-5-benzene of formula (IX) or on a salt of this compound of formula (IX) formed with a strong acid. This salt is preferably formed by combining one mole of the compound of formula (IX) with one mole of a strong monoacid, such as for example HCl or HBr, or by combining two moles of this compound of formula (IX) with a mole of a strong diacid, such as for example H2SO4.

Preferably, this salt is the monohydrochloride of the compound of formula (IX).

 The reaction is advantageously carried out at room temperature, in acetic acid medium, or in lower alkanols such as ethanol or methanol. It can also be carried out at the reflux temperature of the solvents used.

 The compound of formula (IX) may be prepared from 2-bromo-4-trifluoromethyl-6-nitroaniline of formula (X) by reduction of the nitro group to amino group.

This reduction can be carried out by any means known per se to allow the reduction of a nitrobenzene to the corresponding aniline, for example by causing the stannous chloride to act in the presence of concentrated hydrochloric acid, the latter method making it possible to obtain the monohydrochloride of the compound of formula (IX).

 Preferably R "is the dimethylamino radical.

 The combinations according to the invention are preferably and most often of the binary type (only one active substance of group (II)) but sometimes ternary associations (2 active substances of group (II)) or quaternaries (3 substances active group (II)).

 A product in which the ratio by weight of the compound (s) of the group (I) to the compound (s) of the group (II) is between 1: 10,000 and 100, preferably between 1/1000 and 10.

 Of course, these are synergistic associations.

Also it is obvious that this synergy is possible only in the case where one or the other component or both do not present at the chosen dose an activity of 100 Z. The skilled person can easily choose the desired associations.

 However, the invention also extends to associations which while showing only an accessory synergy are included in the general definition of the product.

 For the above purposes, according to a preferred variant, this product according to the invention results from the combination of the compound of group (I) preferably such that R "is the methylamino radical with at least one compound of group (II) consisting of the phosphorus acid derivatives of the general formula (II) described above with all the preferred variants mentioned or by the phosphorous acid itself or one of its alkaline salts.

 Advantageously, the combination will be binary and in all cases we prefer phosétyl-Al or phosphorous acid or its alkaline salts.

 According to this variant, in general, the weight ratio of compound (I): compound group (II) a) is between 0.2 / 1000 and 2, preferably between 1/1000 and 1/2.

 For the purposes of the abovementioned purposes according to another preferred variant, the product according to the invention results from the combination of the compound of group (I) preferably such that R "is the dimethylamino radical with at least one compound of formula (III) described herein. -before with all the favorite variants.

 Advantageously, the combination will be binary and the weight ratio compound group (I): compound of formula (III) is preferably between 5/1000 and 10, preferably between 12/1000 and 6.

 For the purposes of the abovementioned purposes according to a third preferred variant, the product according to the invention results from the combination of the compound of group (I) preferably such that R "is the dimethylamino radical with at least one compound of formula (IV) or ( V) described above with all preferred variants.

 Advantageously, the combination will be binary and the weight ratio compound group (I): compound group (II) is preferably between 5/1000 and 10, preferably between 12/1000 and 6.

 These products according to the invention are intended for simultaneous use, separate or spread over time in fungicidal treatment of plants, including fungicide antimildew.

 In the case of simultaneous use, it is advantageous to use ready-to-use products containing the combination of the active ingredients described above. It is also possible to use products prepared just before use by extemporaneous mixing of the active substances or compositions each containing active ingredients as described below.

 The use can also be spaced in time.

 The product can also be used by treating the cultures to be protected successively by one then the other of the active ingredients (I) and (II) so as to form in situ on the plant the product according to the invention.

The products according to the invention can therefore be used as agricultural fungicides. They are particularly useful for the protection of Solanaceae, tobacco, vine, cucumber, against mildew crops (Phytophtora infestans, Peronospora).
Tabacina, Phytophtora parasitica, Plasmospora viticola,
Pseudoperonospora cubersis).

 They are particularly useful against Solanaceae mildews (tomatoes, potatoes) and cucumbers.

 The products are prepared by simple mixing of the compounds of groups (I) and (II) the constituents.

 For their practical use, the products 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 product according to the invention as previously described in combination with solid carriers (or diluents) or inert liquids, acceptable in agriculture and / or surfactants compatible with the active ingredient, also acceptable in agriculture. In particular, the usual inert carriers and surfactants are usable.

 These compositions are also part of the present invention. They generally contain from 0.5 to 95% of active ingredient. Their content of surfactant is in general between 0 X and 20% by weight.

 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, in particular alkylphenols or arylphenols), salts of sulphosuccinic 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 products are therefore generally in the form of compositions; these compositions according to the invention are themselves in quite diverse forms, liquid or solid.

 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.

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

 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, 0.001 to 20% of active material.

 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 ingredients with pesticidal properties (in particular insecticides or fungicides) or with properties promoting the growth of plants (in particular fertilizers) or with properties regulating plant growth. More generally, the compounds according to the invention can be associated with all the solid or liquid additives corresponding to the usual techniques of formulation.

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

 From these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to crops.

 The concentrated suspensions, which are also applicable in spraying, are prepared in such a way as to obtain a stable fluid product which does not settle and usually contain from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0.5 to 1 to 10% of thisotropic 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 carrier to help prevent sedimentation or as antifreezes for water.

 Wettable powders (or sprayable powder) are usually prepared to contain 20 to 95% of active material, and usually contain, in addition to the solid carrier, 0 to 5% of a wetting agent, 3 To 10% of a dispersing agent and, when necessary, 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents, etc ...

As an example, here is the composition of some emulsifiable concentrates:
Example F (formulation) 1 - active ingredient 400 g / l - alkaline dodecylbenzene sulphonate 24 g / l - nonylphenol oxyethylated A 10 molecules
of ethylene oxide 16 g / l - cyclohexanone 200 g / l - aromatic solvent qs 1 liter
According to another formula of emulsifiable concentrate, it is used
Example F 2 - active ingredient 250 g - epoxidized vegetable oil 25 g - mixture of alkylaryl sulfonate and
of polyglycol ether and fatty alcohols 100 g - dimethylformamide 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.

By way of example, here are various compositions of wettable powders (or powders for spraying)
Example F 3 - active ingredient ................................. 50% - ethoxylated fatty alcohol (wetting agent) 2 , 5 Z - ethoxylated phenylethylphenol (dispersing agent) 5 Z - chalk (inert carrier) ....................... 42.5%
Example F 4 - active ingredient .................................. 10 Z - oxo synthetic alcohol of branched type, in C13
ethoxylated with 8 to 10 ethylene oxide (
wetting) .................................... 0,75% - neutral calcium lignosulfonate (dispersing agent
health ....................................... 12 Z - calcium carbonate (inert load) .... qsp 100 Z
Example F 5: this wettable powder contains the same ingredients as in the previous example, in the following proportions - active ingredient ....................... ............ 75 Z - wetting agent .............................. 1,50 % - dispersing agent ................................. 8 8 Z - calcium carbonate (inert filler) .. ..qsp 100 Z
Example F 6: - active ingredient ................................ 90 Z - ethoxylated fatty alcohol (wetting agent) ......... 4 X - ethoxylated phenylethylphenol (dispersing agent) ... 6 Z
Example F 7 :: - active ingredient * 50 Z - mixture of anionic and nonionic surfactants
ionic (wetting agent) ..................... 2,5 Z - sodium lignosulfonate (dispersing agent) ... 5 X - kaolinic clay inert carrier) 42.5 Z
In order to obtain these spraying powders or wettable powders, the active ingredients are intimately mixed in appropriate mixers with the additional substances and milled with mills to the other suitable grinders. Spray powders whose wettability and setting are then obtained. suspension 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, it is possible to produce tabs. 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 compounds according to the invention may advantageously be formulated in the form of water-dispersible granules also included in the scope of the invention.

 These dispersible granules, with an apparent 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 about 1% and 90%, and preferably between 25% and 90%.

 The rest of the granule is essentially composed of a solid filler and optionally surfactant adjuvants conferring on the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the charge retained is soluble or not in water. When the filler is water soluble, it may be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably mineral, such as kaolin or bentonite. It is then advantageously accompanied by surfactants (at a rate of 2 to 20% by weight of the granule). of which more than half is, for example, at least one essentially anionic dispersing agent, such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder being nonionic wetting agents or anionic compounds such as an alkaline or alkaline earth alkyl naphthalene ulfonate.

 On the other hand, although not essential, other adjuvants such as antifoam agents may be added.

 The granulate according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (dredger, fluid bed, atomizer, extrusion, etc.). It is generally finished by crushing followed by sieving at the particle size chosen within the limits mentioned above.

 Preferably, it is obtained by extrusion, operating as indicated in the examples below.

Example F 8: Dispersible granules
In a mixer, 90% by weight of active ingredient (compound 1) and 10% of bead urea are mixed. The mixture is then milled in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roll extruder. A granule is obtained which is dried, then crushed and sieved so as to keep only the granules with a size of between 150 and 2000 microns respectively.

Example F 9: Dispersible granules
In a mixer, the following constituents - active ingredient (compound nc 1) are mixed ................... 75 Z - wetting agent (alkyl naphthalene sulphonate)
Sodium ........................................... 2% - Cpolynaphthalene dispersing agent sulphonate
sodium) ...................................... 8 Z - inert load insoluble in water (kaolin) ..... 15 Z
This mixture is granulated in a fluid bed, in the presence of water, 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, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active substances, especially fungicides, the latter being in the form of wettable powders, or aqueous granules or suspensions.

 The compounds of formula (I) 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.

 As regards the compositions suitable 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 may contain the active substances according to the invention within very wide limits, ranging from 5.10% to 95% by weight. Their content of surfactant is advantageously between 5 and 40% by weight.

 The doses of use in the case of use as fungicides of the compounds or combination 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 5 to 0.5 Z (percentages by weight).

 The invention also relates to a method for controlling fungal diseases characterized in that one applies one or more times on these plants an effective amount of a product or a composition according to the invention.

 In this process in general, the compound of group (I) is advantageously applied at the rate of 2 g / ha to 250 g / ha (preferably 4 g / ha to 220 g / ha) according to the plants to be treated and the compound of the group (II) of formula (II) from 100 g / ha to 1600 g / ha, preferably from 200 g / ha to 400 g / ha.

 In practice, doses ranging from 5 g / hl to 100 g / hl substantially correspond to doses of active ingredient per hectare of 50 g / ha to about 1000 g / ha.

 The compounds of group (II) of formula (III) (IV) CV) of 50 to 400 g / ha, preferably 55 to 330 g / ha.

 More particularly, the following table summarizes the preferred treatment methods according to the different mildew, geographical areas for Solanaceae and compounds of group (II).

 The examples below, given by way of non-limiting indication illustrate the invention and show how it can be implemented.

EXAMPLE 1 Preparation of dimethylsulfamoyl-1-cyano-2-bromo-4-trifluoromethyl-6-benzimidazole
To a suspension of 1.5 g (0.024 mole) of flaked potash in 80 ml of acetone, 7.0 g (0.024 mole) of 4-bromo-2-cyano-trifluoromethyl is added at room temperature (about 200 ° C). -6 benzimidazole. The gradual dissolution of the reagents and a rise in temperature to 300C are observed. The dissolution is complete after one hour.

 2.6 ml of dimethylsulfamoyl chloride (0.024 mol) are then added to the reaction mixture over a period of 10 minutes and the reaction mixture is stirred for 18 hours and then poured into 1 liter of distilled water. The precipitate obtained is filtered off with suction and then washed with water (4 × 50 ml), then with methanol (50 ml) and finally with ethyl ether (100 ml). After drying, 4.3 g of dimethylsulfamoyl-1-cyano-2-bromo-4-trifluoromethyl-6-benzimidazole (compound A), which melts at 19 ° C., are thus obtained. Yield 45, 1X.

2-cyano-4-bromo-6-trifluoromethyl benzimidazole is prepared as indicated below
To 430 ml of 29 X ammonia A was added over 45 minutes, 50.8 g (0.13 mol) of 4-bromo-2-trichloromethyl-6-trifluoromethylbenzimidazole dissolved in 200 ml of ethanol.

The temperature of the reaction mixture is maintained at 25 ° C. After stirring for one hour at ambient temperature, the reaction mixture is filtered and the filtrate is acidified to pH 1 and then decanted. This oil crystallizes, the solid is washed with water and then dried
There is thus obtained 30.23 g of 2-cyano-4-bromo-6-trifluoromethyl-benzimidazole, melting at 130 ° C.

Yield: 78.4%
Trichloromethyl-2-bromo-4-trifluoromethyl-6-benzimidazole is prepared as indicated below
In a suspension of 81.1 g (0.28 mol) of 1,2-diamino-3-bromo-trifluoromethylbenzene monohydrochloride in 600 ml of acetic acid, 54 ml of methyl trichloroacetimidate are run in half an hour. , A 21 C. The temperature rises to 400C. After 2 hours, crystallization is observed in the reaction medium which is stirred at 200C for 18 hours. The reaction mixture is then poured into 2 liters of distilled water. The precipitate formed is filtered off with suction, washed with water (2 × 200 ml) and then wrung out completely. After prolonged drying, 101 g of 2-trichloromethyl-4-bromo-6-trifluoromethylbenzimidazole, melting at 20 ° C., are obtained. Yield 95 Z.

1,2-diamino-3-bromo-5-trifluoromethylbenzene was prepared in the form of monohydrochloride as indicated below
336 g (1.18 moles) of 2-bromo-4-trifluoromethyl-6-nitroaniline are added in small portions over a period of 1.5 hours to a solution heated to 40 ° C, 840 g of stannous chloride dihydrate in 2.0 liters. concentrated HCl. The temperature rises to 800C. The formation of a large white precipitate is observed. After the end of the addition, the mixture is heated for 1 hour at 800 ° C. and then cooled to 10 ° C. The precipitate formed is collected on a filter, washed with concentrated HCl (400 ml) and then with dichloromethane (2 × 500 ml) and finally air-dried for 2 days.

 There is thus obtained 297 g of 1,2-diamino-3-bromo-5-trifluoromethylbenzene, in the form of monohydrochloride, melting at a temperature above 2700C. Yield 86.3 Z.

 2-Bromo-4-trifluoromethyl-6-nitroaniline was prepared as indicated below.

 In a cooled flask, 900 ml of water are introduced and then 600 ml of concentrated sulfuric acid are added. 150 g (0.73 mol) of 2-nitro-4-trifluoromethylaniline and 117 g (0.73 mol) of bromine are then added over 1 hour 30 minutes. Stirring is continued for 18 hours, then filtered and washed with water. water. After drying, 188.5 g of 2-bromo-4-trifluoromethyl-6-nitroaniline, m.p. Yield 90.6 X.

Example 2 In Vivo Test against Tomato Blight (Phytophthora infestans) on Tomato Plants

 Tomato plants (Lycopersicum esculentum), of Marmande variety, are grown in buckets. When these plants are agitated for one month (5-6 leaf stage, height 12-15 cm), they are sprayed with a suspension or aqueous solution of the test material at the desired concentration. Each tomato plant receives about 5 ml of the solution or dispersion. For each concentration of active ingredient to be tested, the treatment is carried out on two plants.

 This suspension is obtained by mechanically grinding 100 mg of active material in 100 ml of a solution containing 0.05% of Tween 80 (condensate of sorbitan monooleate and 20 ethylene oxide molecules). There is therefore a fungicidal product suspension of 1 g / l. By successive dilutions in distilled water, the desired concentrations are obtained.

 Plants used as witnesses are treated with the same solution but containing no active ingredient.

 After drying for 24 hours, each plant is sprayed by means of an aqueous suspension of Phytophthora infestans spores, responsible for the tomato blight, at a rate of approximately 1 ml / plant (ie approximately 10 05 spores per plant).

 After this contamination, the tomato plants are placed in individual plastic bags in order to avoid interferences between the products and are then incubated for two days at about 150 ° C. in an atmosphere saturated with moisture, then for five days at about 170 ° C. 70% at 90% relative humidity.

Seven days after the contamination, we compare
results obtained in the case of plants treated with
active substance to be tested to those obtained in the case of
plants used as controls.

Interpreting the results by the COLBY method (SR Colby, Weeds, 15 pp. 20-22 (1967))
Disease control is assessed visually by comparing treated and untreated plants counting the number of leaflets affected on the plant relative to the total number of leaflets). For each plant, a percentage of contamination is determined. The efficiency of a product is calculated with the following formula
% control contamination -% treated contamination
E =
% control contamination
In Colby's method, the responses of the fungus to single or associated products are expressed as percentages of effectiveness. Synergy and antagonism can be shown by comparing Eex and Eth.

Eth = A + B - AB where A and B are the
100 percentages of effectiveness
Experimentally observed
at a given concentration
of product A or B
Eex is the percentage of effectiveness of the associated products.

In the case where Eex> Eth, we have a synergy. For this application to remain valid it is necessary that the difference between
Eex and Eth is at least 20 Z.

Results
The results presented in Tables 1 to 3 as well as the curves presented on this occasion, allow to highlight important synergies with the following products: PHOSETYL-AL
METALAXYL
CYMOXANIL
Results
Example 2
1 - Compound of Example 1 + Phosetyl Al

<tb> Products <SEP> concentration <SEP> mg / 1 <SEP> Eex <SEP> Eth <SEP> Eex-Eth
<tb> I <SEP> ex <SEP> 1 <SEP> 1 <SEP> 3 <SEP> 1 <SEP> 70 <SEP> - <SEP> - <SEP>
<tb> t <SEP>"<SEP> | <SEP> 2 <SEP> 1 <SEP> 58 <SEP> t <SEP> - <SEP> - <SEP>
<tb>"<SEP> 1 <SEP> 0 <SEP> - <SEP>
<tb> IPhosetyl <SEP> Al <SEP> | <SEP> t <SEP> 4 <SEP> 000 <SEP> | <SEP> 0 <SEP> - <SEP> - <SEP> t <SEP>
<tb> I <SEP>"<SEP>"<SEP> | <SEP> 2 <SEP> 000 <SEP> 1 <SEP> o <SEP> I <SEP> - <SEP> | <SEP> I <SEP> - <SEP>
<tb>"<SEP> 1000 <SEP> 0 <SEP> - <SEP>
<tb>"<SEP> 500 <SEP> 0 <SEP> - <SEP>
<tb>"<SEP> 250 <SEP> 0 <SEP> - <SEP>
<tb> lex <SEP> I <SEP> + <SEP>) <SEP> | <SEP> 3 <SEP> 3 <SEP> + <SEP> 4 <SEP> 000 <SEP> 1 <SEP> 100 <SEP> 1 <SEP> 70 <SEP> | <SEP> t <SEP> + <SEP> 30 <SEP> 1
<tb> IPhosetyl <SEP> Al <SEP>) <SEP> | <SEP> 2 <SEP> 2 <SEP> + <SEP> 4 <SEP> 000 <SEP> t <SEP> 92 <SEP> t <SEP> 58 <SEP> 1 <SEP> + <SEP> 38 <SEP > 1
<tb> I <SEP>"<SEP> | <SEP> 2 <SEP> + <SEP> 2 <SEP> 000 <SEP> 1 <SEP> 98 <SEP> 1 <SEP> 58 <SEP> 1 <SEP > + <SEP> 40 <SEP> | <SEP>
<tb> X <SEP>"<SEP> | <SEP> 2 <SEP> + <SEP> 1 <SEP> 000 <SEP> 1 <SEP> 91 <SEP> 1 <SEP> 58 <SEP> 1 <SEP > + <SEP> 33 <SEP> | <SEP>
<tb> I <SEP>"<SEP> 1 <SEP> 2 <SEP> + <SEP> 500 <SEP> 1 <SEP> 97 <SEP> | <SEP> 58 <SEP> 1 <SEP> + <SEP > 39 <SEP> | <SEP>
<tb> | <SEP>"<SEP><SEP> 2 <SEP> + <SEP> 250 <SEP> 1 <SEP> 80 <SEP> 1 <SEP> 58 <SEP> 1 <SEP> + <SEP> 22 <SEP> 1
<tb>"<SEP> 1 <SEP> + <SEP> 4000 <SEP> 92 <SEP> 0 <SEP> + <SEP> 92
<tb> I <SEP>"<SEP> 1 <SEP> + <SEP> 2 <SEP> 000 <SEP> 1 <SEP> 84 <SEP> 1 <SEP> 0 <SEP> 1 <SEP> + <SEP > 84
<tb> I <SEP>"<SEP> I <SEP> 1 <SEP> + <SEP> 1 <SEP> 000 <SEP> 1 <SEP> 78 <SEP> 1 <SEP> 0 <SEP> I <SEP > + <SEP> 78 <SEP> 1
<tb>"<SEP> 1 <SEP> + <SEP> 500 <SEP> 93 <SEP> 0 <SEP> + <SEP> 93
<tb> t <SEP>"<SEP> | <SEP> 1 <SEP> + <SEP> 250 <SEP> 1 <SEP> 60 <SEP> 1 <SEP> 0 <SEP> I <SEP> + <SEP > 60 <SEP> 1
<Tb>
The remarkable synergistic effects are clearly shown in view of the table and the curve below. It is recalled that Phosetyl Al is known to be more active against the downy mildew of the vine than against late blight Solanaceae. By cons, in combination with a small amount of the compound of Example 1 there is a remarkable synergy.

Example 3
2 - Compound of Example 1 + Metalaxyl

<tb> Products <SEP> concentration <SEP> mg / 1 <SEP> Eex <SEP> Eth <SEP> Eex-Eth
<tb> | <SEP> ex <SEP> 1 <SEP> 1 <SEP> 3 <SEP> 1 <SEP> 70 <SEP> - <SEP> - <SEP>
<tb> 2 <SEP> 1 <SEP> 2 <SEP> | <SEP> 58 <SEP> 1 <SEP> - <SEP> t <SEP> - <SEP>
<tb>"<SEP> 1 <SEP> 0 <SEP> - <SEP>
<tb> Metalaxyl <SEP> 8 <SEP> 90 <SEP> - <SEP>
<tb>"<SEP> 4 <SEP> 53 <SEP> - <SEP>
<tb> 2 <SEP> .. <SEP> 1 <SEP> 2 <SEP> | <SEP> 25 <SEP> 1 <SEP> - <SEP> t <SEP> - <SEP>
<tb>"<SEP> 1 <SEP> 0 <SEP> - <SEP>
<tb>"<SEP> 0.5 <SEP> 0 <SEP> - <SEP>
<tb> lex <SEP> 1 <SEP> + <SEP>) <SEP>) <SEP> | <SEP> 3 <SEP> 3 <SEP> + <SEP> 2 <SEP> 1 <SEP> 100 <SEP> 1 <SEP> 77.5 <SEP> 1 <SEP> + <SEP> 22.51
<tb> Metalaxyl <SEP>) <SEP> 2 <SEP> + <SEP> 4 <SEP> 100 <SEP> 80 <SEP> 20
<tb> I <SEP>"<SEP> 2 <SEP> + <SEP> 2 <SEP> 1 <SEP> 96 <SEP> 1 <SEP> 69 <SEP> 1 <SEP> + <SEP> 27 <SEP > | <SEP>
<tb> I <SEP>"<SEP> | <SEP> 2 <SEP> + <SEP> 1 <SEP> 1 <SEP> 95 <SEP> 1 <SEP> 58 <SEP> 1 <SEP> + <SEP > 37 <SEP> | <SEP>
<tb>"<SEP>"<SEP> 2 <SEP> + <SEP> 0.5 <SEP> 1 <SEP> 99 <SEP> 1 <SEP> 58 <SEP> 1 <SEP> + <SEP> 41 <SEP> | <September>
<tb> t <SEP>"<SEP> 1 <SEP> + <SEP> 4 <SEP> 1 <SEP> 95 <SEP> 1 <SEP> 53 <SEP> 1 <SEP> + <SEP> 42 <SEP > | <SEP>
<tb> I <SEP>"<SEP> 1 <SEP> + <SEP> 2 <SEP> 1 <SEP> 92 <SEP> 1 <SEP> 25 <SEP> | <SEP> + <SEP> 67 <SEP > | <SEP>
<tb> t <SEP>"<SEP> 1 <SEP> 1 <SEP> + <SEP> 1 <SEP> 1 <SEP> 88 <SEP> 1 <SEP> 0 <SEP> 1 <SEP> + <SEP > 88 <SEP> | <SEP>
<tb>"<SEP> 1 <SEP> + <SEP> 0.5 <SEP> 96 <SEP> 0 <SEP> + <SEP> 96
<Tb>
The remarkable synergistic effects are clearly shown in the table and curve below.

The combination of the metaloxyl with the compound of Example 1 significantly reduces the concentrations of metaloxyl applied.

Example 4
3 - Compound of Example 1 + Cymoxanil

<tb> Products <SEP> concentration <SEP> mg / 1 <SEP> Eex <SEP> Eex-Eth
<tb> ex <SEP> 1 <SEP> 3 <SEP> 70 <SEP> - <SEP>
<tb>"<SEP> 2 <SEP> 58 <SEP> - <SEP>
<tb>"<SEP> 1 <SEP> 0 <SEP> - <SEP>
<tb><SEP> Cymoxanil <SEP> 64 <SEP> 40 <SEP> - <SEP>
<tb>"<SEP> 32 <SEP> 33 <SEP> - <SEP>
<tb>"<SEP> 16 <SEP> 0 <SEP> - <SEP>
<tb> ex <SEP> 1 <SEP> + <SEP>) <SEP> 3 <SEP> + <SEP> 32 <SEP> 100 <SEP> 80 <SEP> + <SEP> 20
<tb> Cymoxanil <SEP>) <SEP> 2 <SEP> + <SEP> 64 <SEP> 98 <SEP> 75 <SEP> + <SEP> 23
<tb>"<SEP> 2 <SEP> + <SEP> 32 <SEP> 98 <SEP> 73 <SEP> + <SEP> 25 <SEP>
<tb>"<SEP><SEP> 2 <SEP> + <SEP> 16 <SEP> 89 <SEP> 58 <SEP> + <SEP> 31 <SEP>
<tb>"<SEP> 1 <SEP> + <SEP> 64 <SEP> 94 <SEP> 40 <SEP> + <SEP> 54 <SEP>
<tb>"<SEP> 1 <SEP> + <SEP> 32 <SEP> 90 <SEP> 33 <SEP> + <SEP> 57 <SEP>
<tb>"<SEP> 1 <SEP> + <SEP> 16 <SEP> 83 <SEP> 0 <SEP> + <SEP> 83 <SEP>
<tb>#<SEP><SEP>"
<Tb>
The remarkable synergistic effects are clearly shown in the table and curves on the following pages.

Thus it is found that the associations according to the invention produce a significant synergistic effect. The synergy level of all the combinations is high compared to the results reported on these associations of other anti-oomycetes.

<tb><SEP> Br
<tb><SEP> II <SEP> n <SEP> con <SEP> 0 <SEP> ~ <SEP> O <SEP> - <SEP> P <SEP> n +
<tb><SEP> CF3 <SEP> I <SEP> 1ot
<tb><SEP> S02R "
<tb><SEP> (I) <SEP> (11)
<tb><SEP> R1 <SEP> - <SE> O <SEP> - <SEP> N <SEP> = <SEP> C <SEP> - <SEP> C <SEP> - <SEP> NH <SEP> - <SEP> C <SEP> - <SEP> NHR2 <SEP> (III)
<tb><SEP> I <SEP> f1 <SEP> (I
<tb><SEP> CN <SEP> O <SEP> 0
<tb><SEP> C2H5 <SEP> - <SEP> NH <SEP> - <SEP> C <SEP> - <SEP> NH <SEP> - <SEP> C <SEP> - <SEP> C <SEP> = <SEP> N <SEP> - <SEP> OCH3 <SEP> Cymoxanil
<tb><SEP> It <SEP> II <SEP> I
<tb><SEP> o <SEP> O <SEP> CN
<tb><SEP> R3 <SEP> C1H3 <SEP> O
<tb><SEP>><SEP> t <SEP> 3 <SEP> li
<tb><SEP>, CH <SEP> -C-OCH3 <SEP> (1V)
<tb><SEP> N
<tb><SEP> CR
<tb><SEP> R7 <SEP> Ct <SEP> 5
<tb><SEP> R7 <SEP> R4 <SEP> 0
<tb><SEP><SEP> C <SEP> - <SEP> R
<tb><SEP>)<SEP> f <SEP> N <SEP>(<SEP> V <SEP>)
<tb><SEP> R
<tb><SEP> R7 <SEP> R4 <SEP> 8
<tb><SEP> 7
<tb> R <SEP> 8 <SEP> o, <SEP>) <SEP> t) S <SEP> AT
<tb><SEP> TO <SEP> AT <SEP> AT
<Tb>

3-oxazolidinonyl 3-butyrolactonyl 3-thiobutyrolactonyl 3-thiooxazolidinonyl

NOMENCLATURE
Cymoxanil 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea.

Metalaxyl N- (12,6-dimethylphenylphenyl) -N- (2-methoxy)
acetyl) -DL methyl alaninate.

Furalaxyl N- (2,6-dimethylphenyl) -N- (2-furanyl)
carbonyl) -DL methyl alaninate.

Benalaxyl N-phenyl acetyl-N-2,6-xylyl-DL-alaninate
methyl.

Oxadixyl 2-methoxy-N- (2-oxo-1,3-oxazolidin-3yl) acet-2 ', 6'
-xylidide.

Phosetyl-Al (see description).

The names are indicated according to the French nomenclature except that the positions of the substituents are indicated before the substituents themselves.

Claims (25)

1) Product resulting from the combination of at least one  compound of group (I) of formula (I) indicated in  description, in which R "represents a radical  dialkylamino having from two to four atoms  carbon with at least one systemic fungicide of the group  (II) constituted in particular by:  (a) phosphorous acid or its alkaline salts or  derivatives of phosphorous acid,  (b) acetamides,  c) acylanilides. 2) Product according to claim 1, characterized in that  the compound of the group (I) is such that R "is the radical  dimethylamino. 3) Product according to claim 1 or 2, characterized in  what results from a binary association. 4) Product according to claim 1, characterized in that  the ratio by weight of the compound (s) of group (I) to  compounds of group (II) is between  1/10000 and 100, preferably between 1/1000 and 10. 5) Product according to one of claims 1 to 4,  characterized in that it results from the association of the  compound of group (I) with at least one compound of  group (II) of formula (II), in which:  R 'is a hydrogen or alkali metal atom or a  alkyl radical containing from 2 to 4 carbon atoms  carbon;  M is a hydrogen atom or an atom of a metal  alkaline, alkaline earth or aluminum;  n 'is an integer of 1 to 3 equal to the valence M,  preferably, when R 'is a hydrogen atom or  of alkali metal, M is an alkali metal and 6) Product according to claim 5, characterized in that  the compound of group (II) is phosphorous acid or a  of its alkaline salts or an alkyl phosphite  preferably Phosetyl Al. 7) Product according to claim 5 or 6, characterized in  what results from a binary association. 8) Product according to one of claims 5, 6 or 7,  characterized in that the compound weight ratio  group (I): compound group CII), is included between  0.2 / 1000 and 2, preferably 1/1000 and 1/2. 9) Product according to one of claims 1 to 4,  characterized in that it results from the association of the  compound of group (I) with at least one compound of  group (II) of formula (III) in which: R1, R2  identical or different represent a grouping  C1 to C13 alkyl, preferably C1 to C4, and  preferably cymoxanil (R1 = CH3, R2 = C2H5). 10) Product according to claim 9, characterized in that  that it results from a binary association. 11) Product according to one of claims 9 or 10,  characterized in that the compound weight ratio  group (I): compound group (II) is between  5/1000 and 10, preferably between 12/1000 and 6. 12) Product according to one of claims 1 or 4,  characterized in that it results from the association of the  compound of group (I) with at least one compound of  group (II) of formula (IV) in which:  R3> R4 identical or different represent a  hydrogen atom or an alkyl group of C1 A  C4, preferably methyl, or C1 alcohol  at C4, advantageously R3 = R4 = methyl.  2-furyl, 5-isoxazolyl, 3-oxazolyl.  having one or two heteroatoms preferably  C5 or C6 heterocycle, preferably C5,  at C6, preferably cyclopropane, or a  chlorine, or R5 represents a cycloalkyl of C3  phenyl, a halogen atom preferably  preferably methoxy, or aryl preferably  is an alcohol group of C1 to C4,  R5 represents a group -CH2-R6 in which R6  3-oxazolidinonyl.  CH3, R5 = -CH2OCH3, R7 = 3-C1, R8 =  R8 = 3-thiobutyrolactonyl, M 12279 or R3 - R4  R3 - R4 to CH3, R7 - H, R5 = CH2OCH3,  -CH 2 OCH 3, R 8 '3-butyrolactonyl, RE 26940 where  where R3 = R4 has methyl, R7 = H, R5 =  cyprofuram, ofurace, CGA 68099 (RE 26745) in  3-thiooxazolidinonyl, advantageously oxadixyl,  3-butyrolactonyl or 3-thiobutyrolactonyl or  preferred and R8 is a 3-oxazolidinonyl ring or  only for formula (IV) with the same variants  R3, R4, R5, R6, R7 have the same meaning  or of formula (V) in which  R5 = 5-isoxazolyl (LAB 149 202 F)  benalaxyl, the compound where R3-R4-CH3, R7-H,  and advantageously, metalaxyl, furalaxyl,  alkyl of C2 to C4, preferably methyl  R7 is an atom of hydrogen, halogen or a radical 13) Product according to claim 12, characterized in that  that it results from a binary association. 14) Product according to one of claims 12 or 13,  characterized in that the compound weight ratio  group (I): compound group (II) is between  5/1000 and 10, preferably between 12/1000 and 6. 15) Product according to one of claims 1 to 14 for a  simultaneous, separate or spread over time  in fungicidal treatment of plants. 16) Use of the products according to one of the claims  1 to 14 as a fungicide. 17) Use of the products according to claim 16 A  as a fungicide for the control of  solanaceae, tobacco, vines and cucurbits. 18) Use according to claim 17, of the products A  as a fungicide for the control of Solanaceae,  especially tomato, potato. 19) Fungicidal composition including antimildiou  characterized in that it contains a product according to  one of claims 1 to 14 and at least one support  inert acceptable in agriculture. 20) Composition according to claim 19, characterized in  it contains 0.5 to 95% of active ingredient. 21) Method for combating fungal diseases of  plants, in particular downy mildew, characterized in that  applies to these plants an effective amount of one  product according to one of claims 1 to 14 or a  composition according to one of claims 19 or 20. 22) Method according to claim 21, characterized in that  the product is applied according to one of the  Claims 5 to 8 or a composition resulting therefrom  according to one of claims 19 or 20 because of  2 to 250 g / ha for the compound of group (I),  100 to 1600 g / ha for the compound (s) of the group (II). 23) Method according to claim 21, characterized in that  the product is applied according to one of the  Claims 9 A Il or a composition resulting therefrom  according to one of claims 19 or 20 because of  2 to 250 g / ha for the compound of group (I),  40 to 400 g / ha for the compound (s) of the group (II). 24) Method according to claim 21, characterized in that  the product is applied according to one of the  Claims 12 to 14 or a composition resulting therefrom  according to one of claims 19 or 20 because of  2 to 250 g / ha for the compound of group (I),  40 to 400 g / ha for the compound (s) of group (II). 25) Process for preparing the product according to one of  Claims 1 to 14, characterized in that mixing  the compound (s) of the group (I) with the  compounds of group (II)