Fungicide and method of its active substance production

A fungicidal composition and a process for the manufacture of an active ingredient ⁷ A fungicidal composition comprising, as an active ingredient, a compound of formula I wherein A is p-chlorophenyl or o, p-dichlorophenyl and X₂ means halogen, or a salt thereof. The invention further relates to a process for the preparation of these active compounds, characterized in that a compound of the formula IIf is admixed with a halogen or mixed halogen molecule. The resulting compound of the formula Uf wherein Hal is halogen is cyclized to a compound of the formula the residue Z is replaced by a 1,2-4-triazol-1-yl residue, whereupon the resulting product is optionally converted into a salt.

270 224

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<td colspan="2"> (11)</td>

<td> (13)</td><td>B2</td>

<td> (51)</td><td>Int. Cl. A 01 N 43/653</td>

<img file="CS270224B2_D0002.tif" />

(Xig)

The invention relates to novel compounds containing a tetrahydrofuran group and a triazole moiety, and to their use for plant protection. The invention further relates to a process for the preparation of these compounds and substances which can optionally be used as intermediates in the process. Further, the invention describes the use of the above compounds as fungicides, fungicidal compositions containing the above compounds as active ingredients, and methods of using the compounds or compositions to combat fungal diseases of useful plants.

Numerous compounds, in particular fungicidal active compounds containing triazole groups, are already known, in particular from European Patent Application Publication No. 151 084, which discloses such compounds corresponding to the general formula

<img file="CS270224B2_D0003.tif" />

where

Tr

Imitation means 1,2,4-triazol-1-yl and represents 1,3-imidazol-1-yl.

SUMMARY OF THE INVENTION It is an object of the present invention to provide compounds having superior properties in post-illness diseases.

It is a further object of the invention to provide compounds which also have a better spectrum of action when used in combating fungal diseases.

It has been found that these objectives can be achieved using the compounds of the invention. These compounds correspond to the general formula I.

<img file="CS270224B2_D0004.tif" />

(I) ve

AND ^X2 wherein it is p-chlorophenyl or o, p-dichlorophenyl and represents a halogen atom.

The invention also encompasses the above compounds in the form of salts. By salts are meant salts required in agriculture, including hydrochlorides, sulphates, oxalates, nitrates and arylsulphonates, as well as addition complexes of the above compounds with metal salts, in particular with iron, chromium, copper, manganese, zinc, cobalt, of tin, magnesium and aluminum.

By way of example, the preparation of zinc-containing complexes is obtained by reacting a compound of formula I with zinc chloride.

It should be noted that the compounds of the invention are not described in the above-cited European Patent Application No. 151,084.

The compounds of the formula I as well as substances which can optionally be used as in-products in the preparation of the compounds according to the invention and which are further defined in the description of the process can exist in isomeric forms, depending on the presence of the center of asymmetry in their molecule. Accordingly, the invention includes all optical isomers as well as racemic mixtures thereof and corresponding diastereomers. The separation of diastereomers and / or optical isomers can be carried out by methods known per se. .

In addition to fungicidal compositions containing the aforementioned compounds as active ingredients, the present invention also provides a process for the preparation of said active ingredients, characterized in that the compound of formula (IIc) is

<img file="CS270224B2_D0005.tif" />

<img file="CS270224B2_D0006.tif" />

(ΙΙβ) in which.

A is as defined above and

Z represents a halogen atom, in an inert solvent adds a halogen or mixed halogen molecule to form a compound of formula Uf

<img file="CS270224B2_D0007.tif" />

(Uf) in which

Hal represents a halogen atom and

A and Z are as defined above, which in the presence of an organic or inorganic base is cyclized to a compound of the formula (Ig)

<img file="CS270224B2_D0008.tif" />

(lig) in which

A, Z and X₂ are as defined above, in which, in the presence of an organic or inorganic base, Z is replaced in a suitable solvent with a 1,2,4-triazol-1-yl residue and the resulting product is optionally converted into a salt.

Suitably, a saturated or halogenated aromatic hydrocarbon is used as the inert solvent for the halogen addition. The halogen or mixed halogen is preferably used in an amount of 1 mole for each mole of the compound of formula (IIc).

The cyclization of the compound of formula (Uf) is preferably carried out at room temperature in the presence of an organic or inorganic base, suitably one of the bases mentioned in the following paragraph for the introduction of the triazole residue. Usually, the molar ratio of the compound of formula (Uf) to the base is preferably between 1.1 and 0.66. The reaction may be carried out in a penetrating or aprotic solvent such as water, an alcohol, a ketone, a nitrile, an ester, a saturated or optionally halogenated aromatic hydrocarbon, dimethylsulfoxide or an amide such as dimethylformamide.

In the next step, the compound of formula (I) is reacted with an unsubstituted triazole in the presence of an organic or inorganic base such as pyridine, triethylamine, sodium hydroxide, potassium hydroxide, alkali metal or alkaline earth metal carbonate or bicarbonate in a suitable solvent such as alcohol , ketone, amide, nitrile or optionally halogenated aromatic hydrocarbon, at a temperature ranging between 80 ° C and the reflux temperature of the solvent used, the molar ratio of the compound of the formula lig to triazole is preferably between 1.1 and 0.2.

Alternatively, the compound of formula (IIc) is first reacted with triazole and then cyclized and halogenated.

The starting materials of the formula (IIc) can be prepared by reacting a haloketone of the formula (IIa) with a general formula of halogen,

<img file="CS270224B2_D0009.tif" />

(IIIa) which has the meaning as v represents an atom in

AND

Z obtained in a manner known per se is reacted with an organometallic compound of formula IIb

<img file="CS270224B2_D0010.tif" />

(lib) in which

M represents, for example, an alkali metal, a magnesium-containing group (MgHal) or a zinc-containing group (ZnHal), * in a solvent selected from preferably ethers such as diethyl ether or tetrahydrofuran and aliphatic, alicyclic or aromatic hydrocarbons such as hexane or toluene at between -50 ° C and the boiling point of the solvent used, the molar ratio of both 11a and 11b being preferably between 1.1 and 0.2. After the reaction is completed and the reaction mixture is not crystallized, the desired compound of formula IIc is obtained.

As mentioned above, the present invention provides fungicidal compositions comprising as active ingredients the above compounds.

The compounds according to the invention can be used for the preventive and curative control of fungi, in particular fungi of the Basidiomycetes, Ascomycetes, Adelomycetes and Fungi imperfecti classes, in particular various rust, mildew, cerkosporios, fusarios, helminthosporios, septorios and rhizoctonios on crops and crops , in particular on cereals such as wheat, barley, rye, oats and their hybrids, as well as rice and maize. The compounds of the invention are particularly active against fungi of the classes Basidiomycetes, Ascomycetes, Adelomycetes and Fungi imperfecti, such as:

Botrytis cinerea (Gray mold),

Erysiphe graminis (Powdery Mildew),

Puccinia recondita,

Piricularia oryzae,

Cercospora beticola,

Puccinia striiformis,

Erysiphe cichoracearum,

Fusarium oxysporum (melonis),

Pyrenophora avenae (brown oatspot),&gt;

Septoria tritici,

Venturia inaequalis (apple scab),

Whetzelinia sclerotiorum,

Monilia laxa

Mycosphaerella fijiensis,

Marssonina panettoniana (lettuce anthracnose),

Alternaria solani (brown blotch of potato leaves),

Aspergillus niger (Aspergillus rot),

Cercospora arachidicola,

Cladosporium herbarium (black cereal),

Helminthosporium oryzae (rice helminthosporiosa),

Penicillium expansum (Penicillium rot),

Pestolozzia sp.,

Phialophora cinerescens,

Phoma betae (heart disease and dry decay),

Phoma foveata,

Phoma lingam,

Ustilago maydis,

Verticillium dahliae,

Ascochyta pisi (pea scab),

Guignardia bidwellii,

Corticium rolfsii,

Phomopsis viticola,

Sclerotinia sclerotiorum,

Sclerotinia minor (sclerotin rot of lettuce),

Coryneum cardinale a

Rhizoctonia solani.

The above compounds of the invention are also effective against the following fungi:

Acrostalagmus koningi,

Alternaria,

Colletotrichum,

Corticium rolfsii,

Oiplodia natalensis,

Gaeumannomyces graminis,

Gibberella fujikuroi,

Hormodendron cladosporioides,

Lentinus degener or tigrinus,

Lenzites quercina,

Memnoniella echinata,

Myrothecium verrucaria,

Paecylomyces varioti,

Pellicularia sasakii,

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

The compounds of the invention are of particular interest because of their broad spectrum of activity in cereal diseases (powdery mildew, rust, blotch, leaf blotch and root rot). The compounds are also of particular interest because of their activity against gray mold (Botrytis) and against cercosporum diseases, and can therefore be applied to a wide variety of useful plants such as vines, vegetables and trees, as well as tropical useful plants such as are peanuts, banana, coffee, pecan, etc.

In addition to the abovementioned application possibilities, the compounds according to the invention also have excellent biocidal activity on a number of other species of microorganisms, including, without limitation, fungi belonging to the following genera:

Pullilaria as P. pullulans, Chaetomium as C. globosum, Aspergillus as A. niger and v.

Conlophora, as a C. puteana species.

Due to their biocidal activity, the compounds of the invention can effectively control microorganisms, the multiplication of which leads to numerous problems in agriculture and industry. In this regard, the disclosed compounds are particularly suitable for the protection of plants or industrial products and equipment such as water, leather, paints, paper, ropes and plastic products and equipment and industrial water supply systems.

The compounds according to the invention are particularly suitable for the protection of lignocellulosic products and, in particular, of wood, whether for timber for furniture purposes or for building timber or timber exposed to weathering, such as wood for building fences and fences, vines and railways frets.

The compounds according to the invention, whether used alone or in the form of the aforementioned wood treatment, are generally used together with organic solvents and can optionally be used in combination with one or more known biocidal products such as pentachlorophenol, metal salts, especially copper, manganese, cobalt, chromium or zinc, derived from inorganic or carboxylic acids (heptanoic, octanoic or naphthenic acids), organic complexes of tin, mercaptobenzothiazole, insecticides such as pyrethroids or organic chloro derivatives,

Finally, the compounds of the invention show excellent selectivity for useful plants.

The disclosed compounds are preferably applied at rates of from 0.005 to 5 kg / ha, in particular from 0.01 to 0.5 kg / ha.

In practice, the active compounds of the invention are rarely used alone, but most often form part of suitable formulations. These compositions, which can be used to protect plants against fungal diseases or as plant growth regulators, contain as active ingredient the compound of the invention described above in admixture with an inert solid or liquid diluent or carrier suitable for agriculture and / or surface-active agents. substances usable in agriculture. In particular, conventional inert carriers and conventional surfactants are used for this purpose.

By carrier is meant organic or inorganic, natural or synthetic material with which the active ingredient is combined to facilitate its application to plants,

CS 270224 82 to their seeds or to or into the soil. Thus, this carrier is generally inert and must be acceptable in agriculture, especially for treated plants. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid mineral fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, liquefied gases, etc.)

The surfactant may be an emulsifier, dispersant or wetting agent of the ionic or non-ionic type. Examples of suitable agents include polyacrylic acid salts, lignosulfonic acid salts and phenolsulfonic and naphthalenesulfonic acid salts, polycondensation products of ethylene oxide with fatty alcohols, fatty acids or fatty series amines, substituted phenols (especially alkylenenols or arylphenols), sulfosuccinic acid ester salts, derivatives taurine (especially alkyl taurates) and phosphoric acid esters with alcohols or condensation products of ethylene oxide with phenols. The presence of at least one surfactant is generally essential if the active ingredient and / or the inert carrier are insoluble in water and water is the vehicle to be used in the preparation of the dosage form.

Thus, the active compounds according to the invention are usually used in the form of compositions. The compositions of the invention may take a wide variety of solid or liquid forms.

Solid formulations include powder formulations for dusting or spreading, in which the active ingredient content can range up to 100 and granules, in particular granules obtained by extrusion, compression, impregnation of a granular carrier or granulation of a powder formulation (active ingredient content V). of these granulates ranges from 1 to 80%).

Forms of liquid compositions or compositions which are formulated into liquid application preparations are solutions, in particular emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or spray powders) and pastes.

Emulsifiable or soluble concentrates most usually contain 10 to 80% active ingredient; whereas the emulsions or solutions suitable for application contain 0.001 to 20% of the active ingredient.

These compositions may also contain various additives, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, complexing agents and the like, as well as other known active substances having pesticidal properties (especially insecticidal or fungicidal properties) which stimulate plant growth (e.g. especially fertilizers) or regulating plant growth. In general, the compounds of the invention may be combined with any solid or liquid additive customary in the art.

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

The dosage used in the application of the compounds or combinations of the invention as fungicides may vary within very wide limits and depends in particular on fungal virulence and climatic conditions.

Compositions containing the active ingredient in a concentration of 0.5 to 5000 ppm are generally very suitable for application purposes. The range of 0.5 to 5000 ppm corresponds to the range of 5.10⁵ % to 0.5% by weight.

The compositions for storage and transport preferably contain from 0.5 to 95 hours by weight of the active ingredient.

Thus, the compositions intended for agricultural applications may contain the active compounds according to the invention in a wide concentration range ranging from 5% to 95% by weight.

The following recipes are given as examples of emulsifiable concentrate compositions. Composition 1 Active ingredient 400 g / liter alkali metal dodecylbenzenesulfonate 24 g / liter nonylphenol condensation product with ethylene oxide containing 10 moles of ethylene oxide g / liter

Cyclohexanone aromatic solvent for

200 g / liter liter

Composition 2 Active ingredient * 250 g epoxidized vegetable oil 25 g mixture of alkylarylsilphonate and polyglycol ether · fatty alcohol 100 g dimethylformamite) 50 g xylene 575 g

Emulsions of any desired concentration which are particularly suitable for foliar application can be obtained from these concentrates by dilution with water.

Suspension concentrates, which can also be applied by spraying, are formulated to form a stable, liquid, non-precipitating product, and usually contain 10 to 75% active ingredient, 0.5 to 15% surfactants, 0.1 to 10% thixotropic agents, 0-10% 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 poorly soluble or not soluble at all. Certain organic solids or mineral salts may be dissolved in the carrier, which additives are intended to aid in the prevention of graying or as antifreeze agents.

Wettable powders (non-spray powders and are generally prepared to contain 20 to 95% of the active ingredient and usually contain_r in addition to a solid carrier, 0 to 5% of a wetting agent, 3 to 10% of a dispersant, and optionally 0 to 5%_r10 % of one or more stabilizers and / or other additives such as penetration agents, adhesives, anti-caking agents, colorants and the like.

Examples of different compositions of wettable (or spray) powders are given in the following section.

Composition 3 of the active ingredient 50% calcium lignosulfonate (deflocculating agent) 5% isopropyl naphthalenesulfonate (anionic surfactant) 1% non-caking silica, 5% kaolin (filler) 39%

Another comminuted powder containing 70% of active ingredient has the following composition:

Simply de 4.

active ingredient700 g sodium dibutylnaphthalenesulfonate50 g condensation product of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde ru 3: 2: 1 kaolin white lazy wettable powder containing

Composition 5 Active substance Lignosulfonate, sodium · Co-u-dibutyliraf talensulfonate Silica

Longer wettable powder with a content of 30 g

100 ALIGN! G

120 g% of active substance has the following composition:

400 gg

G

540 g% of active substance has the following composition:

Composition 6 Active ingredient250 g Calcium lignosulfonate .45 g Mixture of equal parts by weight of white ______ and hydroxyethylcellulose 19g Sodium dibutylnaphthalenesulfonate 15g Silicon dioxide 195g White, 195g Kaolin 281g

Another wettable powder containing 25% active ingredient consists of the following components.

Formulation 7 · Active ingredient 250g Isooctylphenoxy-polyoxyethylenethanol 25g Mixture of equal parts by weight of white and hydroxyethyl cellulose 17g Sodium aluminum silicate 543g Kieselguhr 165g

Another 10¾ wettable powder consists of the following ingredients.

Simply dec 8 active substance100 g mixture of sodium salts of saturated saturated fatty acids 30g condensation product of naphthalenesulfonic acid and formaldehyde 50 · g kaolin 820g

To produce these sprayable or wettable powders, the active ingredient is intimately mixed in a suitable mixer with other ingredients and the mixture is ground in a suitable grinding apparatus. In this way, spray powders are obtained with advantageous wettability and suspensibility. These powders can be suspended in water at any desired concentration and the resulting suspensions can be very advantageously used, especially for application to plant leaves.

Pastes can be produced instead of wettable powders. The conditions and methods of manufacture and use of these pastes are similar to those used with wettable (or spray) powders.

As already mentioned, aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are also within the scope of the invention. The emulsions thus obtained may be of the water-in-oil or oil-in-water type and may also have a thick consistency, such as mayonnaise.

Pellets intended for application to the soil can be produced by agglomeration or impregnation techniques and are usually prepared to have a size between 0.1 and 2 mm &lt;These pellets generally contain 0.5 to 25% of active substances and 0 to 10 ¾ of suitable additives , such as stabilizers, release retarding agents, binders and solvents.

The following is an example of the composition of the composition for making such pellets.

Composition 9 Active ingredient 50g epichlorohydrin2.5g cetyl polyglycol ether2.5g polyethylene glycol 35g kaolin (particle size 0.3-0.8mm) 910g

In this particular case, the preparation is carried out by mixing the active ingredient with epichlorohydrin, dissolving the mixture in 60 g of acetone and adding polyethylene glycol to the solution.

CS 270224 B2 and cetyl polyglycol ether. The resulting solution was moistened with kaolin and the acetone was evaporated in vacuo. Micropellets of this type are preferably used to combat soil fungi.

The compounds of formula (I) may also be used in the form of powders for dusting. For example, a mixture containing 50 g of active ingredient and 950 g of talc or a composition containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc may be used. The above ingredients are mixed, the mixture is ground and applied by dusting.

The following examples illustrate the preparation of the active compounds according to the invention.

He did

Preparation 1 [4-Bromo-2- (2,4-dichlorophenyl) tetrahydrofuran-2-ylmethyl] -1H-1,2,4-triazole (Compounds No. 1a, 1b and 1a + 1b)

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

To a solution of 110 ml of allyl bromide in 700 ml of ethyl ether and 200 ml of tetrahydrofuran at a temperature between 15 and 20 DEG C., 110 g of magnesium are added over a period of 3 hours. The mixture is heated to reflux for 30 minutes, then the liquid phase is decanted off and the residue of the desired organomagnesium derivative is washed with ether.

A solution of 175 g of dG, 2,4-trichloroacetophenone in 250 g of tetrahydrofuran is added to the organic phase at -30 ° C. The reaction mixture was neutralized with acetic acid, washed with water, dried over sodium sulfate, concentrated and the residue was subjected to vacuum distillation. 205 g of a colorless oily product having a boiling point of 140-142 ° C / 4 Pa ​​are obtained.

Step b) Preparation of 1 * 2- (2,4-dichlorophenyl) -2-hydroxypenten-4-yl] -1H-1,2,4-triazole

A mixture of 106 g of the product of step 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 insolubles were filtered off, washed with dimethylformamide and the filtrate was concentrated in vacuo. The residue was dissolved in methylene chloride, the solution was washed with water and concentrated. The residue was dissolved in ethyl acetate and the solution was diluted with heptane to crystallize the product. 97 g of a light pink solid are isolated.

Step c) Preparation of Compounds Nos 1a and 1b

To 35 g of the compound obtained in step b) in 200 ml of chloroform was added bromine at 0 ° C. After decolorization, the solvent was evaporated, the residue was redissolved in methanol α. an aqueous potassium hydroxide solution is added to the solution up to a basic pH. The resulting mixture was evaporated in vacuo, the residue was extracted with ethyl acetate, the extract was washed with water and concentrated. 40 g of an oily material consisting of a mixture of two diastereomers in practically equal amounts are obtained. This mixture was subjected to silica gel column chromatography to isolate the less polar isomer *; 1a in the form of white crystals having a melting point of 83 ° C and then the more polar isomer No. 1b in the form of white crystals having a melting point of 94 ° C. After recrystallization, isomer # 1a melting at 96 ° C and isomer # 1b melting at 104 ° C are obtained. A mixture of equal parts of isomers Nos. 1a and 1b has a melting point of 74 ° C.

The following compounds are also prepared in an analogous manner using the corresponding starting materials:

1- (4-bromo-2- (4-chlorophenyl) tetrahydrofuran-2-ylmethyl) -1H-1,2,4-triazole isomer 1c: mp 74 ° C isomer 1d: mp 78 ° C mixture of isomers 1c * 1d: mp 69 ° C.

Example 2

Preparation of 1- [4-chloro-2- (2,4-dichlorophenyl) tetrahydrofuran-2-ylmethyl] -1H-1,2,4-triazole (Compounds No. 2a and 2b)

Step a) Preparation of 2- (2,4-dichlorophenyl) -1,4,5-trichloro-2-pentanol

A solution of chlorohydrin prepared as described in step a) of Example 1 in 150 ml of dichloromethane at -15 ° C was treated with 13.4 g of chlorine gas. 15 ml of 37% sodium bisulfite was added to the reaction mixture, the resulting mixture was washed with water and evaporated to dryness to give 49.7 g of crude product as a colorless oil containing about 70% of the desired product as a mixture of two diastereomers.

Step b) Preparation of 1- (2,4-dichlorophenyl) -1- (2_/3-dichloro-1-propanyl) oxirane. ·

The first method is to dissolve 10.3 g of the crude chlorohydrin prepared in step (a) of Example 1 above in 30 ml of methanol and add 12 ml of 2.55 x 10 5 methanolic potassium hydroxide solution at room temperature. mol / liter. The precipitate formed is filtered off and the methanolic solution is evaporated in vacuo. The residue was purified by silica gel column chromatography. 7.4 g of a colorless oil are obtained.

According to a second method, 19.9 g of the chlorohydrin prepared in step a) of Example 1 above are dissolved in 75 ml of methanol and a solution of 4.9 g of potassium hydroxide in 20 ml of methanol is added at room temperature. The insoluble material was filtered off and the filtrate was evaporated to give 17.1 g of the epoxide as a yellow oil. This epoxide was treated with chlorine at -15 ° C until the yellow reaction color persisted (10.1 g of chlorine). The mixture was washed first with sodium bisulfite solution and then with water and then evaporated in vacuo. 20.8 g of a yellow oily residue consisting of a 45:55 mixture of two diastereomers are obtained.

Step c) Preparation of 1- (4-chloro-2- (2,4-dichlorophenyl) tetrahydrofuran-2-ylmethyl) -1H-1,2,4-triazole

61.7 g of the epoxide prepared in step b) is heated at 90 DEG C. in 0.5 l of 1-butanol for 6 hours in the presence of 18.6 g of triazolylnithium. The inorganic precipitate was filtered off, the butanol was evaporated and the residue was purified by silica gel column chromatography using a mixture of% ethyl acetate, 48% heptane and 4% methanol as eluent. Gradually, the first diastereomer # 2a with a melting point of 113 ° C and then the second diastereomer # 2b with a melting point of 97 ° C are obtained. A mixture of equal parts of isomers 2a and 2b melts at 90 ° C.

The fungicidal applications of the compounds of the invention are illustrated by the following Examples 3 to 7, but are not intended to limit the scope of the invention in any way.

In these examples, spraying with the solutions or suspensions of the active ingredients is carried out under conditions such that spraying with the solution or suspension at a concentration of 1 g / liter corresponds to an average application of about 2 µg of active ingredient per cn? the leaf area of ​​the treated plant.

Under these conditions used in Examples 3 to 7, the compounds used show no phytotoxicity.

In these examples, if the disease is 80% (but less than 95%) than 80%, and is reported as an average that the test substance provides complete protection against fungal protection is at least 95%, good is the protection at least relatively well denotes at least 70% protection (but below denotes at least 50% (but below 70%).

Unless otherwise indicated, percentages are by weight unless otherwise specified. If percentages are given in connection with stoichiometry, these are percentages molar. In some cases, concentrations are reported in ppm units corresponding to mg / liter.

Example 3

In vivo efficacy test for Botrytis cinerea (tomato) on tomato

By finely grinding the following ingredients: Test drug 60 mg

Tween 80 (surfactant composed of polycondensate ethylene oxide oleate with sorbitan derivative) diluted with water to a concentration of 0.3 ml and made up to a volume of 60 ml with water, prepared as an aqueous emulsion of the test drug. The aqueous emulsion is then diluted with water to the desired concentration.

CS 270224 02

Tomato plants (Marmande variety), grown in a greenhouse, are treated at 30-40 days of age by spraying with the aqueous emulsions prepared as described above containing the test substance in various concentrations. The experiment is repeated twice for each concentration.

After 24 or 48 hours, the leaves are cut from the treated plants and placed in two 14-cm-diameter petri dishes with a moist filter paper on their bottom. Place 5 leaves in each dish. * *

The inoculation is carried out with a spore suspension using a syringe to apply 3 drops of the spore suspension to each leaf. The Botrytis cinerea spore suspension used is obtained from a 15-day-old culture, which is suspended in a nutrient solution (100,000 spores / ml).

The test is evaluated 3 to 6 days after inoculation by comparing the condition of the treated leaves with that of the untreated control. .

Under the conditions described above, the compounds of the present invention, administered at a dose of 1 g / liter, provide good or complete protection: compounds No. 1a, 1b, 1a * 1b, 2a, 2b, 2a * 2b.

Example 4

In vivo potency test for Erysiphe graminis (powdery mildew) on barley After reaching a height of 10 cm, barley plants grown in pots are treated with an aqueous emulsion of the test substance at the concentration indicated below. Each experiment was repeated twice. After 24 hours, the treated barley plants are dusted with spores of Erysiphe graminis (contaminated plants are used for this dusting).

The assay is evaluated 8 to 14 days after inoculation.

Under the conditions described above, the compounds of the invention, administered at a dose of 1 g / liter, provide good or complete protection: compounds No. 1a, 1b, 1a * 1b, 2a, 2b, 2a * 2b.

Example 1

In vivo potency test for Puccinia recondita inducing rust on wheat Plants grown in pots are treated with an aqueous emulsion of the test substance at the concentration indicated below after reaching a height of 10 cm. The experiment is repeated twice for each concentration. ,

After 24 hours, the treated wheat plants were sprayed with a spore suspension of the test organism obtained from the infested plants (50,000 spores / ml). The wheat plants are then placed in an incubation chamber at about 18 ° C and 100% relative humidity for 48 hours.

After these two days, the relative humidity is reduced to 60%. Between 11 and 15 days after inoculation, the condition of the treated plants is evaluated by comparison with the condition of the untreated control plants.

In the above described formulas, the compounds of the invention, administered at a dose of 1 g / liter, provide good or complete protection: compounds No. 1a, 1b, 1a * 1b, 2a, 2b, 2a * 2b. '

Example 6

In vivo potency assay for Piricularia oťyzae on rice. Rice plants grown in pots filled with a mixture of equal parts of peat and tuff are sprayed with an aqueous emulsion containing the test substance at the concentration indicated below after reaching a height of 10 cm. Each experiment was repeated twice. After 48 hours, the treated plants are inoculated with a spore suspension of the test organism prepared from pure culture.

The test is evaluated 8 days after inoculation.

Under the conditions described above, the compounds of the invention, administered at a dose of 1 g / liter, provide good or complete protection: compounds No. 1a, 1b, 1a + 1b, 2a, 2b, 2a * 2b.

Example 7

In vitro potency test for seed-borne fungi and soil fungi

The effects of the compounds according to the invention on the following fungi causing diseases of cereals and other plants are observed:

1) Pyr-nophora avenae (brown oatspot)

2) Sep: oria nodorum '

3) Helninthosporium teres (brown spots of barley) *

4) Fusarium roseum

5) Fusarium nivale. '

6) Fusarium culmorum

7) Rhizoctonia cerealis

8) Septoria tritici

9) Botrytis cinerea (gray mold) sensitive to carbendazim and cyclic imides

10) carbendazim and cyclic imines resistant botrytis cinerea

11) Pseudocercosporella herpotrichoides

12) Fusarium oxysporum F. sp. melonis (Fusarium rot)

13) Rhizoctonia solani (Potato Root)

14) Helminthosporium gramineum (barley stiffness).

In the tables below, these fungi are designated by the numbers above before the name of each fungus.

Each experiment is performed as follows:

The broth, consisting of potato steep liquor, glucose and agar, is placed in a highly supercooled state in a series of Petri dishes (20 ml / dish) previously sterilized in an autoclave at 120 ° C.

During the filling of the dishes, an acetone solution of the active ingredient is injected into the subcooled culture medium in an amount necessary to achieve the desired final concentration.

As controls, the same Petri dishes are used as above, in which the same amount of nutrient medium is added to which no active ingredient is added.

After 24 or 4Θ hours, each of the dishes is inoculated by placing a fragment of mycelium derived from the culture of the fungus in question on the surface of the medium.

The plates were cultured at 22 ° C for 2 to 10 days (depending on the test fungus), after which the growth of the fungus in the plates containing the active substance was compared with that of the control fungus. '

For each of the test compounds, which are generally administered at a dose of 30 ppm, the percentage of inhibition of growth of the test fungus is thus determined. The results are summarized in the following overview.

mushroom

<td>compound no.</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>

<td>Ia</td><td> 100</td><td> 100</td><td> 100</td><td> 95</td><td> 100</td><td> 100</td><td> 95</td>

<td>lb</td><td> 100</td><td> 90</td><td> 100</td><td> 100 ’</td><td> 100</td><td> 100</td><td> 90</td>

<td>la + lr</td><td> 100</td><td> 95</td><td> 100</td><td> 95</td><td> 100</td><td> 100</td><td> 90</td>

<td>2a</td><td> 95</td><td> 95</td><td> 100</td><td> 95 *</td><td> 100</td><td> 100</td><td> 90</td>

<td>2b</td><td> 95</td><td> 90</td><td> 100</td><td> 90</td><td> 95</td><td> 100</td><td> 90</td>

<td>2a + 2:</td><td> 100</td><td> 95</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 95</td>

CS 270224 02