DD281335A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal compositions containing as active ingredient a compound of the formula in which R 1, R 2, R 3, R 4 are identical or different and are optionally substituted for a hydrogen atom or an optionally substituted lower alkyl group, lower cycloalkyl group, aryl group, in particular the phenyl group, X is a halogen atom, n is an integer positive or zero and 6, m0 or 1, preferably 0, Tr is the * and Im is the 1,3-imidazol-1-yl group, n is 1-5 and / or Salt of it. Formula (I)

Description

For this 1 page formulas

Field of application of the invention

The invention relates to novel fungicidal agents for crop protection or industrial use with triazole or imidazole and 2,5-dihydrofuran groups.

Characteristic of the known state of the art

Numerous compounds with triazole groups, especially fungicides, are already known, in particular from EP-A-0 151084.

Object of the invention

An object of the invention is to provide fungicidal compositions having improved properties in the treatment of fungal diseases, especially in cereals, wine and vegetables.

Explanation of the essence of the invention

The object of the invention is the provision of fungicidal agents with an improved range of applications in the field of fungal diseases, especially in cereals.

It has now been found that this object can be achieved by means of agents containing compounds of the formula (I) (which is listed in the list at the end of the description) in which:

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R 4, R, R and R are the same or different and each represents a hydrogen atom or a lower alkyl group, lower cycloalkyl group, lower alkenyl group, especially the allyl group, lower alkenyl group, especially the propargyl group, an aryl group, especially the Phenyl group, which may optionally be substituted by one or more atoms or groups, such as halogen atoms, lower alkoxy groups, aryl groups, in particular phenyl groups, lower alkyl groups, lower haloalkyl groups, in particular the trifluoromethyl group, lower haloalkoxy groups, aryloxy groups, in particular phenoxy groups, or hydroxy groups,

X represents a halogen atom, preferably a fluorine, bromine or chlorine atom, or an alkyl or alkoxy group having up to 12 carbon atoms, preferably having 1 to 4 carbon atoms, which is optionally mono- or polyhalogenated, especially the CF ^ -grip, or a cyano group then,

3 4

when R and / or R stand for a hydrogen atom,

η is an integer, positive or zero and ^ 6, preferably = 2, where / when η 7 is 1, the substituents X may be either the same or different,

Ph = benzene ring, optionally substituted (n = 1 to 5), m = 0 or 1, preferably 0,

Tr is a 1,2,4-triazol-1-yl group and Im is a 1,3-imidazol-1-yl group

means.

The invention also relates to agents containing the agriculturally acceptable salts of the novel compounds. These include the chlorohydrates (hydrochlorides), sulfates, oxalates, nitrates, arylsulfonates or alkylsulfonates and the addition complexes of these compounds with metal salts, especially with iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum salts.

By way of example, complexes with zinc can be obtained by reacting the compounds of formula (I) with zinc chloride.

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As used in the specification, the term "lower" refers to an organic group having at most six carbon atoms. This group can be straight-chain or branched.

The compound of the formula (I) and the compounds which may optionally be used as intermediates in the preparation process, which are described below in connection with this process, may be present in one or more isomeric forms, depending on the number of asymmetric centers in the molecule. The invention therefore also includes all optical isomers and their racemic mixture and the corresponding diastereoisomers. The separation of the diastereoisomers and / or the optical isomers can be carried out in a manner known per se.

For the fungicidal compositions according to the invention, preference is given to the compounds of the formula (I) in which X is a halogen atom and η = 1, 2 or 3.

It has furthermore been found that it is advantageous if, in the case of compounds of the formula (I), η = 1 or 2 and X is a halogen atom bonded in the o- and / or p-position.

It is further preferred that η = 2 and X is a halogen atom bonded in the o- or p-position, advantageously chlorine.

Preferably stand

1 2

R and R each represent a hydrogen atom and advantageously stand

3 4 R and R, which are the same or different, represent a lower alkyl group or

R is a lower alkyl group and

R is a hydrogen atom, or

R is a lower alkyl group and

R is a hydrogen atom.

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Finally, it is also preferred that the compounds contain a 1,2,4-triazol-1-yl group.

The compounds containing in the agents according to the invention can, for. Example, be prepared by a method consisting of the following steps:

3 4

when R and R are each hydrogen, hydrogenation of a compound of formula (IV) in which X, n, m, R and R have the same meaning as in the compounds of formula (I), Hai represents a halogen atom, Pr a protecting group such as 1-ethoxyethyl or a hydrogen

3 4

atom means; or, if R and / or R are not a hydrogen atom, addition of an organomagnesium compound

4 of the formula R MgX to a compound of the formula (IV) and then, if appropriate, addition of an alkyl halide of the formula RX;

Cyclization of the compound of the formula (III) in which R,

R 2, R, R, X, η and m have the same meaning as in the case of the formula I, Hai has the same meaning as in the case of the formula <IV) and Z is a hydrogen atom or OZ is an exiting group;

Introducing or grafting on an imidazole or triazole

ring in / on the compound of the formula (II) in which R,

R 2, R, R, X, m and η have the same meaning as in claim 1 and Y is an atom or a group which can be removed by means of nucleophilic substitution, optionally after appropriate intermediate transformation.

If both substituents R and R represent a hydrogen atom, the compounds of the formula (III) are preferably obtained by hydrogenation of compounds of the formula (IV) with the aid of an equimolar amount of hydrogen in the presence of a suitable catalyst, optionally (partially) poisoned,

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and selected from the following catalysts: palladium, ruthenium, Raney nickel, platinum and rhodium; preferably palladium, optionally (partially) poisoned (pyridine, quinoline), which yields specifically the cis-olefin.

As before, this reaction can be carried out in homogeneous or heterogeneous phase.

Preferably, one selects metallic palladium deposited on an inert support such as activated carbon, calcium carbonate or barium sulfate.

The reaction, while not necessarily required, may be carried out, if desired, advantageously in a polar protic solvent, for example in a lower alcohol such as methanol, or in an aprotic solvent such as in toluene.

The dilution (concentration) of the compound of the formula (IV) is preferably from 1 to 80% by weight or, more preferably, from 5 to 5% by weight, based on the total solution.

Although the molar ratio of catalyst to compound of formula (IV) can vary considerably; However, for obvious technical reasons, the catalyst is preferably used in a molar ratio of 0.01 to 0.5%, based on the compound of the formula (IV).

The reaction is carried out at temperatures in the range of -20 ⁰ C to +150 ⁰ C, preferably in the range of 10 to 8O ⁰ C, and under a pressure of 1 to 10 atm (corresponding to 0.1 to 1 MPa).

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The compounds of the formula (IV) can be obtained by means of generally known processes, for example by addition of the organomagnesium compound of the formula:

R ² - (OPr) CH-CsC-M

in which M is an alkali atom or a magnesium group (Mg-HaI) or a zinc group (Zn-Hal), to an acetophenone of the formula:

(X) Ph (CH ₀ ) -COCH ₀ Hal

η ζ τη ζ

If Pr is a protecting group, it must be split off prior to conversion to the OZ group and cyclization.

The reaction can take place, for example, in a manner known per se in tetrahydrofuran.

3 4

If at least one of the substituents R and R is not a hydrogen atom, the compounds of the formula (III) can

obtained by the addition of a magnesium organo-

4 see compound of the formula R MgX - preferably 2 to 10 mol

to 1 mol of (IV) - to the compounds of general formula (IV), optionally in the presence of copper iodide, preferably at -20 to +80 ⁰ C, and with 0.01 to 5 mol%, optionally subsequently adding an alkyl halide RX (1 to 10 mol

1 mol of compound to which R MgX has been fixed) in a solvent such as tetrahydrofuran, preferably at -20 to

+80 ⁰ C. If the reaction is interrupted by the addition of R MgX, it must of course be followed by hydrolysis on this addition.

In another manufacturing method for the compounds of formula (III) (Z = H) is allowed an organomagnesium compound of the formula R MgHaI to an acetylenic alcohol of

4 12 formula R-C 1 -C-CR R -OH or an organomagnesium compound

4 Forms R MgHaI on an acetylenic alcohol

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Formula RC = C-CR R -OH act in a solvent which is selected from ethers, in particular tetrahydrofuran, or hydrocarbons such as benzene or toluene, in the presence of a copper (II) halide, optionally as a complex with a dialkyl sulfide, and in catalytic amount of 0.1 to 20 mol%, based on the organomagnesium compound R MgHal. This organomagnesium compound is used in twice the molar amount, based on the acetylenic alcohol used, at temperatures of -60 to + 50 ⁰ C, preferably from -30 to + 2O ⁰ C. It is in this way an organomagnesium reactant of the formula ( XIV), according to the information contained in the literature: JF Norman, A. Alexakis, Synthesis (1981) 841-870.

This organomagnesium compound of the formula (XIV) is reacted with a haloacetophenone of the formula (X) Ph (CH_) COCH-Hal.

n 2 m 2

wherein Ph is a phenyl group, under similar conditions as in the preceding methods, whereby the compounds of formula (V), for example, receives.

A compound of the formula (III) can also be converted into a compound of the formula (I) with the aid of the following reaction sequence:

The compound of formula (III) (Z = H) is acylated in a conventional manner, for example with an aliphatic or aromatic acyl halide or with an anhydride in the presence of a base such as pyridine; this leads to the compound (III) (Z = acyl); the latter compound is then condensed with an azole to give a compound (XIII) starting from a compound (III) under the conditions described below;

- the group Z is then saponified under the usual conditions;

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the cyclization of (XIII) can then be carried out as described below;

in the specific cases, especially when X denotes a substitution of the aromatic ring in the o-position and m = 0, the compounds (I) are obtained directly from the compounds (III) (Z = acyl) under the conditions of condensation of the Azols are obtained, and the compounds (XIII) (Z = acyl) are then not isolated.

An advantageous, but not obligatory method of synthesizing compounds of the formula (II) in which Y is a hydrogen atom is to cyclize the compound of the formula (III) in cis form, where X, n, m,

2 3 4

R, R and R have the same meaning as for the compounds of formula (I) either in acidic medium when Z is a hydrogen atom or in basic medium when Z is an leaving group such as a mesylate, tosylate , Triflate group or a group of the formula [Ph ₃ P ⁺ - 0 -].

These leaving groups are bound in a known manner and selectively to the OH group without touching the tertiary OH group.

For this cyclization, the organic or inorganic acid catalysts are suitable. They may be soluble or insoluble in the reaction medium as well as protic or aprotic. As protic acids can be mentioned hydrochloric or hydrochloric acid, sulfuric acid, trifluoroacetic acid, perchloroacetic acid, benzenesulfonic acid, toluenesulfonic acid and methanesulfonic acid. Examples of aprotic acids are Lewis acids, such as BF, AlCl ₃ and SnCl.

Preferably, from 0.1 to 2 molar equivalents of acid are used.

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It is also possible to carry out this cyclization with the aid of catalysts which are bound to inert supports, for example with sulfone resins or resins with sulfonic acid groups.

The cyclization is usually carried out by simply heating the indicated reactants. The temperature is generally in the range of 10 to 100 ⁰ C or, when a solvent is present, in the range of 10 ⁰ C to the boiling temperature of the solvent used.

As examples of the many useful solvents, mention may be made of the aliphatic and aromatic solvents, such as toluene, ethers and ketones.

In the case of cyclization in basic medium, there may be exemplified inorganic bases such as sodium hydroxide or potassium hydroxide, alkali metal or alkaline earth metal carbonates, nitrogen bases such as triethylamine, quaternary amines such as tetrabutylanonoxum hydroxide or phosphonium hydroxides. Preferably, 0.01 to 2 molar equivalents of base are used. It is also possible to carry out this cyclization with the aid of catalysts bound to inert supports, such as resins. The reaction is usually carried out at a temperature in the range of 10 to 100 ⁰ C and optionally in the presence of a solvent, such as the aliphatic and aromatic solvents, ethers and ketones.

The compounds of the formula (II) in which Y is an OH group can be obtained by basic treatment of compounds of the general formula (III) in which Z is H.

In this case, the reaction proceeds via the corresponding epoxides as intermediates which are obtained from the compounds of general formula (VI). It is then necessary after the isomerization, the group Y = OH in a leaving group, such as the mesylate, tosylate or triflate or

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Ph ₃ P -O, before the substitution reaction with the triazole can take place, as described below.

The grafting is advantageously carried out in the presence of an acid acceptor, in an anhydrous or non-anhydrous medium, in a solvent inert under the reaction conditions, and generally at a temperature between 50 and 180 ^° C., preferably at a temperature close to the boiling temperature of the solvent. Suitable acid acceptors are inorganic bases, such as sodium hydroxide or potassium hydroxide, alkali metal or alkaline earth metal carbonates, nitrogen bases, such as triethylamine, quaternary amines, such as tetrabutylammonium hydroxide, or the phosphonium hydroxides. The solvents used are advantageously aprotic polar solvents, for example dimethylformamide, dimethylacetamide, dimethylsuloxide, acetone, methyl ethyl ketone, acetonitrile, N-methylpyrrolidone or protic polar solvents, such as methanol or propanol. If desired, this reaction can be carried out in the presence of a suitable catalyst. Suitable catalysts include phase-transfer catalysts, such as quaternary ammonium compounds such as the tetrabutyl ammonium halides, preferably the iodides.

The reaction is preferably carried out with a molar excess of triazole or imidazole compound of preferably 1.05 to 1.5.

If a solvent is also used, preference is given to working in a dilute medium containing 1 to 70% by weight of compound of the formula (II), based on the total solution.

The acid acceptor is present in at least a stoichiometric amount based on equivalents of the mobile hydrogen of the triazole or imidazole compounds. Generally, a ratio of 1 to 2.5 molar equivalents is satisfactory.

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The salt compound of triazole or imidazole can be prepared independently, and in this case, the presence of an acid acceptor in the grafting reaction is not required. This preparation is carried out in anhydrous or non-anhydrous medium in a solvent under the same operating conditions as described for the in situ formation of the triazole or imidazole in its salt form.

Another preparation method is that a haloacetophenone of the formula (X) Ph (CH-) COCH_Hal with a

η 2 m, 2 _{3 4}

organometallic compound of the formula R R C = CR - CHR M,

12 3 4

in which X, m, n, Hal, R, R, R, R and M have the abovementioned meaning, in a solvent, preferably selected from ethers such as diethyl ether or tetrahydrofuran, aliphatic, alicyclic or aromatic hydrocarbons such as hexane or toluene in a Temperature in the range of -50 ⁰ C to the reflux temperature of the solvent and in a molar ratio of ketone to organometallic compound of preferably 1.1 to 0.2. The reaction leads to the compound of formula (V) after neutralization of the reaction medium.

Subsequently, the compound of formula (V) is reacted with an unsubstituted imidazole or triazole in the presence of an organic or inorganic base such as pyridine, triethylamine, sodium hydroxide, potassium hydroxide, alkali carbonates and bicarbonates and alkaline earth carbonates and bicarbonates and in a suitable solvent such as the alcohols, Ketone, amides, nitriles, optionally halogenated aromatic hydrocarbons, at a temperature of 80 ⁰ C to the reflux temperature of the solvent and in a molar ratio of compound (V) to imidazole or triazole of preferably 1.1 to 0.2; this leads to the compound of formula (VI). The reaction generally proceeds via an epoxide intermediate of formula (VII), which may optionally be isolated or prepared separately by methods known per se.

12 lAo-61 677

To the compound (VI) is preferably added halogen or a halogen mixture in a molar ratio of 1: 1 in an inert solvent such as saturated or aromatic, optionally halogenated hydrocarbons; this leads to the compound (VIII). The compound (IX) is preferably obtained at room temperature by cyclization of the compound (VIII) in the presence of an organic or inorganic base as stated above in a molar ratio of the compound (VIII) to the base of preferably 1.1 to 0.66. The reaction may be carried out in a protic or aprotic solvent such as water, alcohol, ketone, nitrile, ester, saturated or aromatic, optionally halogenated hydrocarbon, dimethyl sulfoxide or amide such as dimethylformamide.

Another method of preparing compounds (IX) is to graft the imidazole or triazole ring after cyclization using the same procedure for the various steps. Thus, to the compound (V), 1 mol of halogen or halogen halide (halogen mixture) is added to form the compound (X); this is then cyclized to compound (XI), in which subsequently a triazole or imidazole group is introduced, so that the compound (IX) is obtained.

In order to obtain the compound (I), the compound (IX) is reacted with a base. Suitable inorganic bases include sodium hydroxide or potassium hydroxide, alkali metal or alkaline earth metal carbonates, nitrogen bases such as triethylamine, quaternary amines such as tetrabutylammonium hydroxide or phosphonium hydroxides. Preferably, 1 to 5 molar equivalents of base are used per mol of compound (IX). The reaction is advantageously carried out in the presence of a solvent. Suitable solvents are advantageously polar aprotic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, N-methyl

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pyrrolidone or protic polar solvents such as methanol or propanol or butanol. The temperature generally ranges from room temperature to the reflux temperature of the solvent.

According to another method, the triazole or imidazole ring is grafted onto compound (IV) or (III) to give compounds of formula (XII) or (XIII); then, in the case of compound (XII), hydrogenation is carried out and then cyclized under the same conditions as indicated above.

The compound of the formula (XIII) (Z = H) can also be obtained by reacting an azolyl-acetophenone obtained by grafting a triazole or imidazole ring onto the haloacetophenone of the formula (X) Ph (CH ₂ ) COCH-Hal under the conditions mentioned above has been obtained with an organomagnesium compound of the formula (XIV).

Another method is to treat the compound of formula (X) with an imidazole or triazole in the presence of an excess of base (2 moles or more). This leads directly to the compound of formula (IX).

It is also possible to halogenate the compound (VII) and then graft the azole (imidazole or triazole) to obtain the compound (VIII).

After completion of the reaction is - regardless of the method used - the resulting compound from the reaction medium by any means known, for example, by distilling off the solvent or by crystallizing the compound in the reaction mixture or by filtration; then, if necessary, this compound is purified by conventional methods, for example by recrystallization from a suitable solvent.

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The agents according to the invention can be used both preventatively and for controlling fungi, especially against Basidiomycetes, Ascomycetes, Adelomycetes or Fungi imperfecti, especially against the rust diseases, mildew, foot disease of the grain, fusariosis (rot), Helminthosporiosum- or Streak diseases, spot diseases, root diseases of crops and plants in general, and in particular cereals such as wheat, barley, rye, oats and their hybrids, and rice and maize. The compounds according to the invention act in particular against fungi, especially against Basidiomycetes, Ascomycetes, Adelomycetes or Fungi imperfecti, such as Botrytis cinerea, Erysiphe graminis, Puccinia recondita, Piricularia oryzae, Cercospora beticola, Puccinia striiformis, Erysiphe cichoracearum, Fusarium oxysporum (melonis) , Pyrenophora avenae, Septoria tritici, Venturia inaequalis, Monilia laxa, Mycosphaerella fijiensis, Marssonina panettoniana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzi-ia sp, Phialophora cinerescens, Phoma betae, Phoma foveata , Phoma lingam, Ustilago maydis, Verticillium dahliae, Ascochyta pisi, Guignardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia sclerotiorum, Sclerotinia minor, Coryneum cardinale, Rhizoctonia solani.

They also act 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,

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Phellinus megaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, les Stereum, Stilbum sp. Trametes trabea, Trichoderma pseudokoningi, Trichothecium roseum.

The compositions according to the invention are of particular interest because of their broad spectrum of action in cereal diseases (mildew, rust, foot disease, streak and spot diseases and rot). They are also very important because of their action against gray rot (botrytis) and against leaf spot diseases and can therefore be applied both to numerous crops such as wine, vegetables and tree plantations as well as to tropical crops such as peanut, banana trees, coffee trees, Pekan walnut and others. be applied.

In addition to the applications already mentioned, the agents according to the invention also have an excellent biocidal activity against numerous other types of microorganisms, among which fungi, for example of the species:

Pullularia such as P. pullulans, Chaetomium such as C. globosum, Aspergillus such as A. niger, Coniophora such as C. puteana, can be named.

Because of their biocidal activity, the compositions of the invention enable effective control of microorganisms whose multiplication poses numerous problems in the agricultural and industrial sectors. In this respect, they are particularly well suited for the protection of plants or industrial products such as wood, leather, paints, paper, cordage, plastics and industrial water pipes.

They are particularly well-suited for the protection of products based on lignocellulose, especially wood, and indeed

16 lOo-61 677

wood for furniture as well as lumber or wood that is exposed to the elements of weather such as fence or lumber, wooden pegs in vineyards or railway sleepers.

The compositions of the invention which are used for the treatment of wood, are generally used with organic solvents and may optionally with one or more known biocidal products such as pentachlorophenol, metal salts, especially copper, manganese, cobalt, chromium, zinc salts of Mineral acids or carboxylic acids (heptanoic acid, octanoic acid, naphthenic acid), organic tin complexes, mercaptobenzothiazole, insecticides such as pyrethroids or organochlorine compounds can be combined.

Finally, they have excellent selectivity to the crops.

They are advantageously applied in dosages of 0.005 to 5 kg / ha, in particular from 0.10 to 0.5 kg / ha.

The compositions of the invention useful for the protection of plants against fungal diseases or for controlling plant growth contain as active ingredient a compound as described above in combination with either agriculturally acceptable solid or liquid carriers and / or surface-active agents. In particular, the usual inert carriers and conventional surfactants are useful.

In this specification, "carrier" is an organic or inorganic, natural or synthetic material with which the active ingredient can be combined in order to achieve its application to the plant, to seed or to the soil.

17 lOo-61

easier. This carrier is thus generally inert, and it must be agriculturally compatible, especially tolerated by the treated plant. The carrier can be solid, such as clays, natural or synthetic silicates, silicic acid, resins, waxes, solid fertilizers, etc., or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquified gases, etc.

The surfactant may be an emulsifier, dispersant or wetting agent, ionic or non-ionic in nature. Mention may be made, for example, of the salts of polyacrylic acids, of lignosulfonic acids, of phenolsulfonic acids or naphthalenesulfonic acids, polycondensation products of ethylene oxide and fatty alcohols or fatty amines, substituted phenols, especially alkylphenols or arylphenols, the salts of sulfosuccinic acid esters, taurine derivatives, especially alkyl taurates, phosphoric esters of polyoxyethylated Alcohols or phenols. The presence of at least one surfactant is generally required when the active ingredient and / or the inert carrier are not water-soluble and water is used as the carrier in use.

The agents of the invention may take on very different solid or liquid forms.

As forms for solid agents are called: powders for dusts or scattering agents, containing up to 100% compound of formula (I), and granules, especially those by extrusion, by compression, by impregnation of a granulated carrier or by granulation granules obtained from a powder, the content of the compound of formula (I) being 1 to 80% in the latter cases.

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As forms of liquid agents or agents which are liquid in the application, solutions, in particular the water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders or wettable powders and pastes may be mentioned.

The emulsifiable or soluble concentrates usually contain 10 to 80% of active ingredient, the ready-to-use emulsions or solutions containing 0.01 to 20% of active ingredient.

These agents may additionally contain any other ingredients, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers and scavengers, as well as other known agents having pesticidal properties, especially insecticides or fungicides, or having properties that promote the growth of the plants , especially fertilizers or plant growth regulating properties. In general, the compounds of the invention may be combined with any solid or liquid additive that conforms to the usual procedures for preparing such agents.

For example, in addition to the solvent, if desired, the emulsifiable concentrates may contain 2 to 20% of suitable additives such as stabilizers, surfactants, penetrants, corrosion inhibitors, dyes or the aforementioned adhesives.

The application doses of the compositions according to the invention in the case of use as fungicides can vary within wide limits and are mainly based on the virulence of the fungi and the climatic conditions.

Generally, agents that contain 0.5 to 5000 ppm of active ingredient are generally suitable. This information applies to the ready-to-use agent. The range of 0.5 to 5000 ppm corresponds to 5 χ 10 to 0.5 wt .-%.

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The storable and transportable agents advantageously contain 0.5 to 95 wt .-% active ingredient.

The intended for agricultural use means according to the invention can thus contain the active compounds according to the invention within very wide limits, from 5 χ 10 to 95 wt .-%.

embodiments

The following gives the composition of some concentrates:

example 1

- Active substance

- Alkalidodecylbenzenesulfonate

- Condensation product of nonylphenol and 10 moles of ethylene oxide

- Cyclohexanone

- aromatic solvent ad 11.

According to another formula for an emulsifiable concentrate, one uses:

Example 2

- Active substance

- epoxidized vegetable oil

- Mixture of alkylarylsulfonate and ethers of polyglycol and fatty alcohols

- dimethylformamide

- xylene

Starting from these concentrates, it is possible by dilution with water to produce emulsions of any desired concentration, which are particularly suitable for application to the foliage.

400 g / i 24 g / i 16 g / i 200 g / i

250 G 25 G 100 G 50 G 575 G

20 lOo-61,677

The suspension concentrates, which can also be sprayed, are made to give a stable flowable product which does not settle out; they usually contain 10 to 75% active ingredient, 0.5 to 15% surfactants, 0.1 to 10% thixotropic agents and 0 to 10% suitable additives such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrants and adhesives and as a carrier water or an organic Liquid in which the active substance is little or insoluble; certain solid organic or mineral salts may be dissolved in the carrier to help prevent sedimentation or as antifreeze for the water.

The wettable powders or wettable powders are usually prepared to contain 20 to 95% active ingredient; they usually contain, in addition to the solid support, 0 to 5% of a wetting agent, 3 to 10% of a dispersant and, if necessary, 0 to 10% of one or more stabilizers and / or other additives such as penetrants, adhesives or anticaking agents, dyes etc.

As an example, various compositions for wettable powders are given here.

Example 3

- active ingredient 50%

- Calcium lignosulfonate

(Deflocculant) 5%

- Isopropylnaphthalenesulfonate

(anionic wetting agent) 1%

- Silica

to prevent clumping 5%

- Kaolin (filler) 39%.

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Another spray powder with 70% active ingredient contains the following components:

Example 4

- Active ingredient 700 g

Sodium dibutylnaphthylsulfonate 50 g

- Condensation of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde in the ratio 3/2/1 30 g

- kaolin 100 g

- Chalk from Champagne 120 g.

Another spray powder with 40% active ingredient contains the following components:

Example 5

- Active ingredient 400 g

Sodium lignosulfonate 50 g

Sodium dibutylnaphthalenesulfonate 10 g

- Silica 540 g.

Another composition of a spray powder with 25% active ingredient is as follows:

Example 6

- Active substance

- Calcium lignosulfonate

- Mixture of equal parts by weight of chalk from Champagne and hydroxyethylcellulose

- sodium dibutylnaphthaiine sulfonate

- Silica

- Chalk from Champagne

- kaolin

250 G 45 G 19 G 15 G 195 G 195 G 281 G

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Another spray powder with 25% active ingredient contains the following components:

Example 7

- Active ingredient 250 g

- Isooctylphenoxy-polyoxyethylene-ethanol 25 g

- Mixture of equal parts by weight of chalk from Champagne and hydroxyethylcellulose 17 g

Sodium aluminum silicate 543 g

- Diatomaceous earth 165 g.

For another spray powder with 10% active ingredient, the following components are used:

Example 8

- Active substance

- Mixture of sodium salts of saturated fatty acid sulfates

Condensation product of naphthalenesulfonic acid and formaldehyde

- kaolin

In order to obtain these wettable powders or wettable powders, the active ingredients are thoroughly mixed in appropriate mixers with the additional substances and comminuted and ground with mills or other suitable comminution equipment. In this way, spray powders are obtained which are advantageously wettable and suspendable. It is possible to prepare aqueous suspensions of any desired concentration and these suspensions can be used very advantageously, above all on the foliage of the plants.

100 G 30 G 50 G 820 G

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Instead of wettable powders you can also make pastes. The conditions and modalities of preparation and use of these pastes are similar to those of wettable powders or wettable powders.

As already stated, the aqueous dispersions and emulsions, for example the agents obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are within the general scope of the invention. The emulsions may be water-in-oil or oil-in-water emulsions and have a thick mayonnaise-like consistency.

The granules for application to the soil are usually prepared so that their dimensions are 0.1 to 2 mm, and they can be prepared by agglomeration or impregnation. Generally, the granules contain 0.5 to 25% active ingredient and 0 to 10% additives such as stabilizers, release retarders, binders and solvents.

According to one example of the composition of a granulate, the following constituents are used:

Example 9

- Active ingredient 50 g

- Epichlorohydrin 2.5 g

- Cetyl polyglycol ether 2.5 g

- Polyethylene glycol 35 g

- kaolin (grain size 0.3 to 0.8 mm) 910 g.

In this particular case, the active ingredient is mixed with the epichlorohydrin and dissolved in 60 g of acetone; then the polyethylene glycol and the cetyl polyglycol ether is added. Then the kaolin is sprayed with the resulting solution and finally the acetone is removed in vacuo. Such a microgranule

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lat is advantageously suitable for controlling the soil fungi and the penthogenic fungi which infest the stems and parts in the air, when applied to the soil or in water, especially in paddy fields.

The compounds of formula (I) may also be used in the form of powders for dusts. It is also possible to use an agent containing 50 g of active ingredient and 950 g of talc. Furthermore, one can use an agent containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc. Mix and grind these ingredients and apply the mixture by means of dusts.

The following examples illustrate the preparation of the active substances contained in the agents according to the invention.

Production Example 1

Preparation of 2- (2,4-dichloro-1-phenyl) -2-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran.

Into a 50 ml flask under inert atmosphere was added a solution of 1.001 g (3.80 mmol) of 2-chloromethyl-2- (2,4-dichloro-1-phenyl) -2,5-dihydrofuran in 1.00 g of N- Methylpyrrolidone (NMP) submitted. Then 314.8 mg (4.56 mmol) of 1,2,4-triazole and 630.2 mg (4.56 mmol) of potassium carbonate were added. The reaction mixture was heated at 170 ^° C. for 14 hours and then cooled to about 20 ^° C. Then 10 ml of toluene and then water saturated with ammonium chloride were added. The toluene phase was separated and the aqueous phase was extracted twice more with 10 ml of toluene. The combined organic extracts were dried over sodium sulfate. Filtration and concentration under reduced pressure gave a semi-crystalline residue which was purified.

673 mg (2.28 mmol) were obtained; Mp (Kofler) 107 ⁰ C. Yield: 60%, based on the amount of 2,5-dihydrofuran compound.

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Preparation of г-Спіогте ^ уі-г- (2,4-dichloro-1-phenyl) -2,5-dihydrofuran.

In a 100 ml flask under an inert atmosphere, 10 g (35.5 mmol) of 1-chloro-2- (2,4-dichloro-1-phenyl) -3-pentene-2,5-diol (cis isomer) in Submitted to 60 ml of toluene. 0.5 g of p-toluenesulfonic acid was added and heated to reflux temperature. After completion of the reaction was washed and separated. This gave 9.36 g (35.5 mmol) of a brown oily residue. Yield: 100%, based on the starting compound.

Preparation of 1-chloro-2- (2,4-dichloro-1-phenyl) -3-pentene-2,5-diol (cis isomer).

Method A:

Into a 500 ml flask under an inert gas atmosphere was added a solution of 24 g of 1-chloro-2- (2,4-dichloro-1-phenyl) -5- (1-ethoxyethoxy) -3-pentyne-2-ol in 150 ml of toluene and 0.613 g of palladium - 5% on charcoal. Then hydrogen was introduced under atmospheric pressure at 25 ⁰ C. After 2 hours, filtered and the solvent removed under reduced pressure.

The oily residue was taken up in 200 ml of methanol and treated with 50 ml of 0.5N hydrochloric acid. Then, the methanol was removed under reduced pressure to obtain 19.36 g of an oily orange residue.

By adding 10 ml of ethyl acetate and then 35 ml of pentane, 5.35 g (19.3 mmol) of the desired diol were precipitated.

Preparation of 1-chloro-2- (2,4-dichloro-1-phenyl) -5- (1-ethoxyethoxy) -3-pentyne-2-ol

In a 500 ml flask under an inert atmosphere containing 13.37 g of magnesium and 30 ml of tetrahydrofuran was allowed in the course of 2 1/2 hours 54.5 g (0.5 mol) of bromoethane, dissolved in 225 ml of THF at T = 30 ⁰ C, run in. The resulting solution was

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then added dropwise over 1 hour at room temperature to a solution of 64.09 g (0.5 mol) of 2-ethoxyethyl-propargyl ether in 40 ml of THF. (0.4 mol) 2,4,2'-trichloroacetophenone, to this solution then a solution of 89.4 g at 0 ⁰ C in the course of 2 hours in 100 ml of THF. The whole was kept for 6 hours at 20 ⁰ C. It was then cooled to 0 ^° C. and 28.6 ml (0.5 mol) of acetic acid were added thereto over 15 minutes at 5 ^° C., then 150 ml of water and then 100 ml of ethyl ether were added. The organic phase or layer was washed twice with 50 ml of water and once with 50 ml of brine; then the solvents were removed under reduced pressure. This gave 136.6 g of a viscous yellow oil

 Yield: 97.2%, based on the starting compound.

Method B:

In a 1 1 flask containing under inert atmosphere 36.5 g (1.5 mol) of magnesium and 216 g of THF and 75 ml of toluene, was allowed at 30 ⁰ C in the course of 1 1/4 hours 163.45 g of bromoethane in 250 ml of toluene ». The whole was allowed to rest for 15 minutes at 24 ⁰ C. Then, a solution of 42.15 g (0.75 mol) of propargyl alcohol in 50 ml of toluene was added dropwise over 1 1/2 hours. Then, a solution of 111.7 g (0.5 mol) of 2,4,2'-trichloroacetophenone in 100 ml of toluene was added dropwise at 44 ⁰ C. The whole was allowed to rest at room temperature. It was then cooled to 0 ⁰ C and treated dropwise with 90 g (1.5 mol) of acetic acid. It was then evaporated, 250 ml of toluene was added and washed with dilute sulfuric acid and then with water. The organic layer was then concentrated, cooled, precipitated, filtered and dried. L-chloro-2- (2,4-dichloro-l-phenyl) afforded -3-pentyn-2,5-diol, mp = 90 ⁰ C.

The hydrogenation was carried out in the same manner as in Method A, but at 50 ^° C. The desired diol was obtained.

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Preparation of the compound of Example 1 according to another method.

Stage a)

Preparation of 1-chloro-2- (2,4-dichlorophenyl) -4-penten-2-ol.

An organomagnesium compound was prepared by adding a solution of 110 ml of allyl bromide in 700 ml of ethyl ether to 200 ml of tetrahydrofuran with 110 g magnesium in the course of 3 hours at 15 to 20 ⁰ C. Then, 30 minutes, heated under reflux, decanted, the organic phase removed and the residue washed with ether.

At -30 ⁰ C a solution of 175 gл / 2,4-trichloroacetophenone was added in 250 g of tetrahydrofuran, and neutralized with acetic acid. It was then washed with water, dried over sodium sulfate, concentrated and then distilled in vacuo. This gave 205 g of a colorless oil with bp 140 to 142 ° C / 0.04 bar (3 χ 10 ~ ² mmHg).

Stage b)

Preparation of 1- 2 - {(2,4-dichlorophenyl) -2-hydro-4-pentenyl] -1H, -1,4,4-triazole.

A mixture of 106 g of product of stage a), 55 g of triazole and 160 g of potassium carbonate was heated to 120 ^° C. in 600 ml of dimethylformamide for 4 hours. The insoluble fractions were filtered off, washed with dimethylformamide and the reaction mixture was concentrated in vacuo. The residue was dissolved in methylene chloride, the solution was washed with water and then concentrated. The compound crystallized from the ethyl acetate after addition of heptane. 97 g of a pale pink solid melting at 101 ⁰ C were obtained.

Stage c)

Preparation of 1- £ 4-bromo-2- (2,4-dichlorophenyl) tetrahydro-2-furanyl! Methyl] -IH, 1, 2, 4-triazole.

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35 g of the compound obtained in step b) in 200 ml of chloroform were treated at ⁰ ° C. with bromine. After decolorization, the solvent was evaporated and the residue redissolved in methanol. Potassium hydroxide was added thereto until the pH became basic. After evaporation of the mixture in vacuo, the residue was extracted with ethyl acetate, the extract was washed with water and concentrated. The resulting oil (40 g) consisted of a mixture of the two diastereoisomers in substantially equal proportions. By chromatography on silica successively isolated the less polar isomers la in the form of white crystals, which melted at 83 ° C, and then the more polar isomers Ib in the form of white crystals, which melted at 94 ⁰ C. Recrystallization gave la with melting point 96 ^° C. and Ib with melting point 104 ^° C.

Stage d)

Preparation of 2- (2,4-dichloro-1-phenyl) -2-methyl (1-triazolyl) 2,5-dihydrofuran.

In a 250 ml Kolbemwurden 30 g (795 mmol) of isomer A, 200 ml of methanol and 10.4 g (159 mmol) KOH in cookies ä presented 85%. The reaction mixture was refluxed for one hour, cooled, filtered, and the filtrate was concentrated. The residue was dissolved in 200 ml of chloroform, the solution filtered and evaporated. The semi-solid residue was recrystallized from ethyl acetate with 20% heptane. This gave 19.4 g of the compound with mp 107 ⁰ C.

Production Example 2

Preparation of 2- (2,4-dichloro-1-phenyl) -2- (methyl-1,2,4-triazol-1-yl) -4-n-propyl-2,5-dihydrofuran.

(Compound no.2)

In a 1 liter flask under nitrogen, a mixture of 7.8 ml (0.132 mol) of propargyl alcohol, 2.6 g (0.014 mol) of CuI- and

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submitted dry tetrahydrofuran, which was cooled to -1O ⁰ C. Then, an organomagnesium compound dropwise added at this temperature, which was prepared from 34.4 g (0.28 mol) of propyl bromide and 7.2 g (0.30 mol) of magnesium in 120 ml of tetrahydrofuran. After 15 hours at room temperature, a solution of 23.6 g (0.106 mol) of 2,4,2'-trichloro-acetophenone in 140 ml of tetrahydrofuran was added dropwise. After 2 hours, the mixture was neutralized with glacial acetic acid, poured into water and extracted with ether; the ether extract was dried and then evaporated. This gave 17 g of an orange oil consisting essentially of 2- (2,4-dichlorophenyl) -1-chloro-propyl-S-cis-pentene-2,5-diol and in the presence of 5.6 ml of acetic anhydride was acetylated in 30 ml of pyridine. After standing overnight at room temperature, the pyridine was stripped off together with the toluene and the residue was heated at 130 ^° C. for 3 hours in the presence of 25 g of potassium carbonate and 7 g of triazole in 250 ml of dimethylformamide. The whole was filtered, the filtrate concentrated, diluted with water and extracted with dichloromethane. After evaporation of the solvent, the residue was chromatographed on silica, eluent: ethyl acetate / heptane 1: 1, to give compound 2 as pale yellow crystals, which melted at 85 ° C; Yield 4.2 g.

Production Example · 3

Preparation of 2- (4-chlorophenyl) -2- (methyl-1,2,4-triazol-1-yl) -4-ethyl-2,5-dihydrofuran.

(Compound no.3)

The same procedure was followed in the above example using 27.2 g (0.25 mol) of ethyl bromide and 20.8 g (0.11 mol) of 4,2'-dichloroacetophenone. After condensation with the triazole, no cyclization was carried out and substantially the monoacetate of crude 2- (4-dichlorophenyl) -1- (1,2,4-triazol-1-yl) -4-ethyl-3-cis was obtained pentene-2,5-diols (20 g

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a black oil). This compound was then saponified with 5.8 g of KOH in 250 ml of methanol at reflux. Evaporation, dilution with water, extraction with dichloromethane and evaporation in vacuo gave 17.5 g of a black oil. This was dissolved in 200 ml of dry dichloromethane and treated with 4.9 ml of methanesulfonyl chloride and then added dropwise at -30 ⁰ C with triethylamine. After 2 hours, the mixture was washed with water, concentrated, and the residue, after being dissolved in 200 ml of methanol, was treated with 3.8 g of KOH. After extracting with ethyl acetate and washing with water, the crude residue was chromatographed, eluent: ethyl acetate / heptane 1: 1. The desired compound was readily identified by its intense staining upon development with iodine after thin layer chromatography. Compound 3 was obtained in the form of a partially crystallized brown oil. According to the above procedures, the compounds of formula (XV) were prepared.

^X l ^Y l R ³ R ⁴ Fp ⁰ C 1 Cl Cl H H 107 2 Cl Cl n-propyl H 85 3 Cl H ethyl H oil 4 Cl H H H 124 5 Cl Cl ethyl H 86.5 6 Cl H n-propyl H 7 Cl Cl 4-F-Phenyl H 8th Cl Cl phenyl H 9 Cl Cl allyl H 10 Cl H allyl H 11 Cl Cl 3-F-propyl H 12 Cl H 3-F-propyl H 13 Cl Cl cyclopentyl H 14 Cl H cyclopentyl H 15 Cl Cl allyl CH-

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2- (2,4-dichloro-l-phenyl) -2-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran

2- (2,4-dichloro-1-phenyl) -n-propyl-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- (4-chloro-1-one) phenyl) -4-ethyl-2-methyl- (1,2,4-triazol-l-yl) -2,5-dihydrofuran

2- (4-chloro-l-phenyl) -2-methyl- (1,2,4-triazol-l-yl) -2,5-dihydrofuran

2- (2,4-dichloro-1-phenyl) -ethyl-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- (4-chloro-1-phenyl) ^ -n-propyl ^ -methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- {2,4-dichloro-1-phenyl) ^ -F-phenyl-methylmethyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- (2,4-dichloro-1-phenyl) -phenyl-methyl- (1,2,4-triazole-1-one) yl) -2,5-dihydrofuran 2- (2,4-dichloro-1-phenyl) -allyl-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- ( 4-chloro-1-phenyl) -4-allyl-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- (2,4-dichloro-1-phenyl) -SFn- propyl-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- (4-chloro-1-phenyl) -SFn-propyl-methyl- (1,2,4-) triazol-1-yl) -2,5-dihydrofuran 2- (2,4-dichloro-1-phenyl) -cyclopentyl-methyl- (1,2,4-triazol-1-yl) -2,5- dihydrofuran 2- (4-chloro-1-phenyl) -cyclopentyl-methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran 2- (2,4-dichloro-1-phenyl ) ^ -allyl-S-methyl ^ -methyl- (1,2,4-triazol-1-yl) -2,5-dihydrofuran.

Application example · 1

In vivo test against Erysiphe graminis on barley (barley powdery mildew).

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Barley seeded in garden soil in small pots, after becoming 10 cm high, was sprayed with an aqueous emulsion or spray mixture of the active substance to be tested, which had the following composition:

- Connection 1, 2, 3, 4 nzw. 5: 60 mg

Tween 80 (surfactant) consisting of an oleate of a polyoxyethylene derivative of sorbitan as a 10% solution in water: 0.3 ml

- Water ad 60 ml.

This aqueous emulsion was then diluted with water to the desired concentration. The experiment was repeated twice. After 24 hours, the barley plantlets were pollinated by means of sick plants with spores of Erysiphe graminis. 8 to 14 days later, the results were noted.

Under these conditions, complete protection was achieved with compounds 1, 2, 3, 4 and 5 at a dose of 1 g / L.

Application Example · 2

In vivo test against Puccina recondita, responsible for the rust disease of wheat.

Wheat seedlings sown in garden pots in small pots were sprayed after being grown 10 cm high with aqueous emulsions or spray mixtures of the same composition as given in Application Example 1.

After 24 hours, an aqueous spore suspension (50,000 spores per ml) was sprayed onto the wheat plantlets. This suspension was obtained from diseased plants. Subsequently, the pots were kept with the wheat plants for 48 hours in an incubation at about 18 ⁰ C and 100% relative humidity. After these 2 days, the relative humidity was reduced to 60%. The control of the condition

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planting occurred between the 11th and 15th day after contamination by comparison with untreated control plants.

At a dose of 1 g / L, complete protection was achieved with compounds 1, 2 and 5.

Application example 3

In vivo test against Piricularia oryzae, responsible for rice pissicular rice.

Rice plants seeded in pots in a 50/50 mixture of enriched peat and pozzolan were sprayed 10 cm at the growth stage with an aqueous emulsion or spray mixture as defined above and the concentration given below. The experiment was repeated twice. After 48 hours, a suspension of spores obtained in pure culture was applied to the leaves.

The evaluation was made 8 days after the contamination. Under these conditions, the test compounds 1, 2, 3, 5 at a concentration of 1 g / l provided complete protection.

Application Example 4

In vivo test against Botrytis cinerea of tomato.

By fine grinding, an aqueous suspension of the active ingredient was prepared, which was to be tested, having the following composition:

- Active substance 60 mg

Tween 80 (surfactant consisting of a monolaurate of a polyoxyethylene derivative of sorbitan) 0.6 ml

- water 60 ml

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This aqueous suspension was then diluted with water to the desired concentration.

In the greenhouse pulled tomato plants (variety Marmande), 60 to 75 days old, were sprayed with aqueous suspensions of the composition described above with an active ingredient concentration of 1 g / l (1000 ppm). For each concentration, the experiment was repeated twice.

After 24 hours, the leaves were cut and placed in 2 petri dishes (11 cm in diameter) on the bottom of which had been placed a piece of damp filter paper (5 leaflets per dish).

The inoculum, an aqueous spore suspension, was then added dropwise via syringe (3 drops per leaflet). This spore suspension of Botrytis cinerea had been obtained from a 15 day old culture which was then suspended in a broth (80,000 units per ml). The control or observation is carried out 4 to 6 days after the contamination by comparison with a non-treated control. In this way, the percentage protective effect, based on the untreated control plants was determined.

Under these conditions, it was observed that complete protection was obtained with the compounds Nos. 2 and 5 in a concentration of 0.33 g / L.

Application Example 5

In vitro test against seeds, fungi and soil fungi.

The effect of the compounds according to the invention on the following fungi responsible for diseases in cereals and other plants was investigated:

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11) Pyrenophorae avenae

6) Septoria nodorum

12) Helminthosporium teres 9) Fusarium roseum

8) Fusarium nivale

7) Fusarium culmorum

13) Rhizoctonia cerealis

14) Septoria tritici

1) Botrytis cinerea, sensitive to carbendazim and the cyclic imides

2) Botrytis cinerae, resistant to carbendazim and the cyclic imides

5) Pseudocercosporella herpotrichoides

3) Fusarium oxysporum F.sp melonis

4) Rhizoctonia solani

10) Helminthosporium gramineum.

The above numbers serve to identify the fungi in the table below.

Each experiment was carried out in the same way as follows: A nutrient medium consisting of potato, glucose and agar (PDA medium), was in supercooled state in a series of Petri dishes (20 ml per dish) after sterilization in an autoclave at 12O ⁰ C. brought in.

When filling the dishes, an acetonic solution of the drug was injected into the medium to obtain the desired final concentration.

The control was analogous Petri dishes containing equal amounts of nutrient medium, but no active ingredient.

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After 24 or 48 hours each shell was filled with a mycelium fragment derived from a previous culture of the fungus in question.

The dishes were maintained at 22 ° C for 2 to 10 days, depending on the fungus being tested, and then the growth of the fungus in the dishes containing the drug to be tested was compared to the growth of the same fungus in the control dish.

In this way, for each compound tested, the degree of growth inhibition of the fungus in question was determined at a dose of 30 ppm.

11 6 12 9 8 7 13 14 1 2 5 3 4 10

95 95 100 90 90 100 95 100 100 100 100 80 80 100 95 90 100 80 100 100 95 95 95 90 80 90 35 90 95 90 50 50 90 90 80 90 100 50 50 90 100 90 100 90 90 100 100 - 100 100 100 100 80 100 90 100 90 50 90 95 80 90 100 100 80 80 90

Claims (5)

A fungicidal composition, characterized in that it comprises an active ingredient in combination with at least one inert agriculturally acceptable carrier, wherein the active ingredient is a compound of formula (I) or a salt thereof, in the R ¹ , R ² , R ³ , R ^{4 are the} same or different and each represents a hydrogen atom, a lower alkyl group, lower cycloalkyl group, aryl group, especially the phenyl group, optionally with one or more atoms or groups such as halogen atoms, lower alkoxy group , Aryloxy or aryl groups, lower alkyl or haloalkyl groups, lower haloalkoxy groups or hydroxy groups; X is a halogen atom, preferably a fluorine, bromine or chlorine atom, or an alkyl or alkoxy group having 1 to 12 carbon atoms, preferably having 1 to 4 carbon atoms, which is optionally mono- or polyhalogenated, especially the CF ₃ group, or a cyano group, when R ³ and / or R ^{4 is} a hydrogen atom, η is an integer, positive or zero and 6, preferably = 2, where, when η is 1, the substituents X may be either the same or different, m = 0 or!, preferably 0, Tr represents a 1,2,4-triazoMyl group and represents a 1,3-imidazol-1-yl group. 2. Composition according to claim 1, characterized in that X is a halogen atom, preferably a chlorine atom, and η = 1,2 or 3. 3. Composition according to claim 2, characterized in that η = 2 and preferably X is bound in o- and p-position. 4. Composition according to claim 1, characterized in that
R ¹ and R ² each represent a hydrogen atom and R ³ and R ⁴ , which are the same or different, represent a lower alkyl group or R ³ represents a lower alkyl group and R ⁴ is a hydrogen atom, or R ^{4 represents} a lower alkyl group and R ³ is a hydrogen atom. 5. Composition according to claim 1, characterized in that it contains 0.5 to 95% active ingredient.