CS266339B2 - Fungicide and process for preparing active compounds - Google Patents

Description

The present invention provides a novel plant protection compound comprising a triazole moiety and oligoether groups, and combinations thereof with certain fungicides. The invention also relates to a process for the preparation of this compound and its application in the protection of plants, in particular with regard to combating parasitic fungi, as well as to the use of said compound and its above-mentioned combinations for controlling plant growth.

Numerous compounds, especially fungicides, containing a triazole moiety are already known, in particular from European Patent Application No. 151 084.

It is an object of the invention to provide compounds and combinations thereof that exhibit improved potency and / or selectivity. ·

It is a further object of the invention to provide compounds and combinations which can be used not only for combating fungi on cereals, but also for combating fungi on grapevines, on garden crops and in particular on fruit trees, and against fungi causing cereal rust.

Another object of the invention is to provide compounds and combinations with reduced risk of toxicity compared to known products.

It has been found that these objectives can be achieved by the use of a compound of the invention corresponding to formula I

and their agriculturally acceptable salts.

The subject of the invention is a fungicidal composition, characterized in that it contains the above-mentioned compound of the formula I or a salt thereof as active ingredient.

The compound of the invention may exist in two diastereomeric forms. The invention encompasses both a mixture of these diastereomeric forms and individual diastereomers. The separation of these diastereomers is carried out using methods known per se. .

The invention also relates to salts of a compound of the invention, in particular hydrochloride, sulfate, oxalate, nitrate or arylsulfonates, and addition complexes thereof with metal salts, in particular iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum. The product group consisting of the compound of formula (I), its diastereomers and its derivatives will be referred to hereinafter as a compound of the invention by plural.

One or more compounds of the invention may also be combined with at least one fungicide selected from Group II, including the following subgroups:

1. chlorinated or nitrated benzene derivatives, such as quintozene or chlorothalonil,

2. dicarboxamide derivatives such as captan, folpet, captafol, iprodione or procymidone;

3. derivatives containing one or more heterocyclic rings such as quinolines (ethoxyquin), morpholines (dodemorph, tridemorph, fenpropimorph) and piperidines (fenpropidine);

CS 266 339 B2

4. phosphorous acid derivatives such as metal phosphites such as phosethyl-Al and phosphorous acid itself;

5. dithiocarbamic acid derivatives such as maneb, mancozeb or zineb;

6. phenol derivatives such as dinocap or binapacryl;

7. quinone derivatives such as dithianone or chloranil;

8. carbamic acid and benzimidazole derivatives such as carbendazim, benomyl and thiophanate-methyl;

9. sulfur derivatives such as dazomet or etridiazole or sulfur alone;

10. amines and amides such as dichlorane, carboxin, triforine, cymoxanil, metalaxyl and ofurace;

11. diazines such as quinomethionate, fenarimol, anilazine, nuarimol, bupirimat, ethylrimol and pyrazophos;

12. sulfamides such as dichlorofluanid and tolylfluanid,

13. guanidines, such as doguadine,

14. triazoles, for example compounds described in British Patent Specification 2,046,260, such as diniconazole or other known triazoles, propiconazole, triadimephone, triadimenol, diclobutrazole, bitertanol, penconazole and flutriafol;

15. imidazoles such as prochloraz or imazalil;

16. Cyanobenzimidazoles, such as those described in French Patent Specification No. 2,521,141;

17. Copper or organic or inorganic copper derivatives.

The Group II active ingredients are known active ingredients, most of which are described in expert papers such as The Pesticide Manual (The British Crop Protection Council, 7th Edition, 1983).

The above combinations are mostly of the binary type (one Group II active substance), but in some cases ternary combinations (two Group II active substances) or quaternary combinations (three Group II active substances) are also used.

Among these known active substances, preparations of subgroups 1, 2, 4, 5, 6, 7, 8, 9 and 17 are preferred.

Preferred active ingredients of Group II are also the following preparations: chlorothalonil, iprodione, fenpropimorph, tridemorph, fenpropidine, dinocap, diathianone, menab, mancozeb, zineb, phosethyl-Al, cymoxanil, nuarimol, captan, carbendazim, captafol, sulfur, copper copper, such as copper oxychloride or copper quinolate.

The chemical names of the above preparations are summarized as follows:

chlorothalonil tetrachloroisophthalonitrile iprodion 3- (3,5-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide

fenpropimorph (+) -cis-4-SZ- (4-tert-butylphenyl) -2-methylpropyl-2,6-dimethylmorpholine

CS 266 339 B2

tridemorph 2,6-dimethyl-4-tridecylmorpholine fenpropidine 1-C3- (p-tert-butylphenyl) -2-methylpropyl] piperidine dinocap 2- (1-methylheptyl) -4,6-dinitrophenyl crotonate dithianon 5,10-Dihydro-5,10-dioxonaphtho-C2,3-b3-1,4-dithiaanthraquinone maneb Manganese ethylenebis (dithiocarbamate)

mancozeb zinc salt complex with maneb preparation *** zineb zinc ethylenebis (dithiocarbamate) phosethyl-Al aluminum tris-O-ethylphosphonate captan N- (trichloroethylthio) cyclohex-4-ene-1,2-dicarboximide carbendazim methyl 1-benzimidazol-2-ylcarbamate

captafol

N- (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1,2-dicarboximide cymoxanil

2-cyano-NC (ethylamino) carbonyl-2- (methoxyimino) acetamide nuarimol alpha- (2-chlorophenyl) -alpha- (4-fluorophenyl) -5-pyrimidinemethanol diniconazole 1- (2,4-dichlorophenyl) -4, 4-dimethyl-2- (1,2,4-triazol-1-yl) -1 * penten-2-one. (this product is described in the aforementioned British Patent Specification 2,046,260).

The weight ratio of the compound of the invention to the active compound of group II as defined above is preferably between 0.000 3 and 3000, in particular between 0.001 and 1000.

The present invention also provides a process for the preparation of the active ingredient of the above formula I, characterized in that trifluoroethanol (CF 3 -C 3 OH) is reacted with a compound of formula IV

(IV) wherein

R ³ represents an alkyl group having 1 to 4 carbon atoms or both R ³ together form an alkylene radical having 2 or 3 carbon atoms, in the presence of an acid catalyst.

The acid catalyst used in this reaction may be a protic or aprotic acid.

Suitable protic acids include hydrochloric acid, sulfuric acid, trifluoroacetic acid, perchloric acid, benzenesulfonic acid, toluenesulfonic acid or methanesulfonic acid. Suitable aprotic acids include

Lewis acids such as boron trifluoride, aluminum chloride and tin tetrachloride. While using

The hydrochloric acid catalyst may be prepared in situ, for example with the aid of an acyl chloride, in particular acetyl chloride, which reacts with the alcohol present to produce hydrogen chloride.

The reaction is usually carried out simply by heating the reactants. The temperature generally ranges from 50 ° C to the boiling point of the reaction mixture. The solvent is generally the trifluoroethanol present in the reaction mixture, but it is also possible to use an inert co-solvent, in particular an aliphatic, alicyclic or aromatic hydrocarbon, optionally halogenated, or an ether.

The compounds of formula IV can be obtained by methods known per se.

_M Alternatively, a compound of formula I prepared by reacting a compound of the formula II

in which

Z represents a chlorine or bromine atom, reacted with an alkali metal triazole derivative, for example a sodium or potassium salt, or a quaternary ammonium or phosphonium derivative of the triazole.

The reaction is usually carried out in a polar aprotic solvent and can also be catalysed, for example by addition of an alkali metal iodide. The reaction temperature is generally between 50 and 250 ° C, preferably between 70 and 230 ° C. For economic reasons, a total concentration of reactants of between 1 and 50% is most often used.

Compounds of formula II may be prepared by reacting trifluoroethanol with a compound of formula III

Cl

CH ₂ Z (III) wherein they are as defined above, in the presence of an acid catalyst.

The aforementioned combinations of compounds of the invention with one or more Group II fungicides, hereinafter referred to as combinations of the invention for simplicity, are prepared by simply mixing the respective components.

The compounds and combinations according to the invention can be used for both preventive and curative control of fungi, in particular of the class Basidiomycetes, Ascomycetes, Adelomycetes or

Fungi imperfecti, in particular rust, powdery mildew, root rot, fusarios, helminthosporios, septorios and root diseases caused by fungi of the genus Rhizoctonia on vegetables and plants in general,

In particular, to combat fungal diseases of cereals such as wheat, barley, rye, oats and their hybrids, as well as rice and maize.

In particular, the compounds of the invention are active against the fungi disclosed in European Patent Application No. 151 084 and are also active against the following fungi:

Acrostalagmus koningi,

Alternaria,

Colletotrichum (anthracnose),

Corticium rolfsii,

Diplodia natalensis (diplodium rot),

Gaeumannomyces graminis,

Gibberella fujikuroi (fusariocsa),

Hormodendron cladosporioides,

Lentinus degener or tigrinus,

Lenzites quercina,

Memnoniella echinata,

Myrothecium verrucaria,

Paecylomyces varioti,

X. Pellicularia sasakii,

Phellinus megaloporus,

Polystictus sanguineus,

Poria vaporaria,

Sclerotium rolfsii (sclerotia rot),

Stachybotris atra,

Stereum (silvery),

Stilbum sp.,

Trametes trabea,

Trichodera pseudokoningi (rot rot) a

Trichothecium roseum (bitter rot).

The compounds and combinations according to the invention are of particular interest because of their broad spectrum of action in cereal diseases (powdery mildew, rust, root rot, helminthosporiosis, septoriosis and in particular fusariosis, which are difficult to combat). Also of particular interest is the efficacy of the aforementioned compounds and combinations against Botrytis and cercosporiosis, and can therefore be applied to a wide variety of crop plants such as grapevines, garden crops, fruit trees and tropical crop plants. such as peanuts, banana palm, coffee tree, date palm, coconut palm, pecan, etc.

The compounds and combinations of the invention show excellent selectivity for useful plants.

In addition to the efficacy described above, the compounds and combinations of the present invention also exhibit excellent biocidal activity against a variety of other microorganisms, including, but not limited to, fungi such as genera of the genera.

Pullularia such as P. pullulans, Chaetomium such as C. globosum, Aspergillus such as Aspergillus niger and Coniophora such as C. puteana.

Due to their biocidal activity, the compounds and combinations of the invention can be used to effectively combat microorganisms whose proliferation causes numerous problems in agriculture and industry. These products are therefore particularly suitable for the protection of plants or plants

CS 266 339 B2 industrial products such as wood, leather, paints, paper, ropes and ropes, plastics and industrial waters.

Said compounds and combinations are particularly suitable for the protection of lignocellulosic products, in particular wood, such as furniture wood, timber or weathered wood, such as wood fences and fences, such as timber, vine supports or railway sleepers.

The compositions or combinations according to the invention, which are used either as such or in the form of the above-defined agents for the treatment of wood, can optionally be combined with one or more known biocidal substances such as pentachlorophenol, metal salts, in particular copper, manganese, cobalt, chromium or zinc, derived from inorganic acids or carboxylic acids (heptanoic, octanoic or naphthenic acids), organic tin compounds and mercaptobenzthiazole.

The active compounds described are generally applied in doses of from 0.005 to 5 kg / ha, preferably from 0.01 to 5 kg / ha, in particular from 0.05 and especially from 0.1 to 2 kg / ha.

The use of at least one compound of the invention in combination with iprodione is particularly useful in combating cereal and seed diseases such as leaf diseases.

The use of at least one compound of the invention in combination with fenpropidine is particularly useful in combating cereal and seed diseases such as leaf diseases.

The use of at least one compound of the invention in combination with fenpropimorph is particularly useful in combating cereal and beet diseases.

The use of at least one compound of the invention with tridemorph is of particular interest for combating cereal diseases.

Of course, ternary or quaternary mixtures containing the aforementioned compounds can also be used for the above purposes.

Thus, a ternary mixture comprising fenpropimorph, iprodione and a compound of the invention or a tridemorph, iprodione and a compound of the invention is particularly suitable.

The use of at least one compound of the invention in combination with maneb is particularly suitable for combating diseases of vegetables, fruit trees, small fruits and vines.

The use of at least one compound of the invention in combination with mancozeb is particularly suitable for combating diseases of vegetables, fruit trees, small fruit and grapevine.

The use of at least one compound of the invention in combination with zineb is particularly suitable for combating diseases of vegetables, fruit trees, small fruit and grapevine.

The use of at least one compound of the invention in combination with sulfur is particularly suitable for combating diseases of vegetables, fruit trees, small fruit and grapevine. .

The use of at least one compound of the invention in combination with dinocap is particularly suitable for combating diseases of vegetables, fruit trees, small fruit and grapevine.

Of course, ternary or quaternary mixtures containing the aforementioned compounds can also be used for the above purposes.

The use of at least one compound of the invention in combination with carbendazim is particularly suitable for combating diseases of fruit trees and small fruits, vegetables and cereals.

CS 266 339 B2

The use of at least one compound of the invention in combination with captafol is particularly suitable for combating diseases of cereals, fruit trees and small fruit and potatoes.

The use of at least one compound of the invention in combination with captan is particularly suitable for combating diseases of cereals, fruit trees and small fruit.

The use of at least one compound of the invention in combination with dithianone is particularly suitable for combating fruit tree and small fruit diseases.

The use of at least one compound of the invention in combination with mancozeb is particularly suitable for combating fruit tree and small fruit diseases.

The use of at least one compound of the invention in combination with copper is particularly suitable for combating fruit tree and small fruit diseases.

Of course, ternary or quaternary mixtures containing the aforementioned compounds may also be used for the above applications.

The use of at least one compound of the invention in combination with chlorthalonil is particularly suitable for combating diseases of vegetables, cereals, beets and potatoes.

The use of at least one compound according to the invention in combination with diniconazole is of particular interest for combating dustiness on cereals, in particular dustiness on barley and wheat (Ustilago nuda).

In practice, the compounds and combinations of the invention are rarely used alone, but most often form part of the respective compositions of the invention. These compositions which can be used to protect plants against fungal diseases or to control plant growth contain, as an active ingredient, a compound of the invention as described above in combination with a solid or liquid, agriculturally acceptable carrier and / or surfactant which: it is also agriculturally acceptable. In particular, customary inert carriers and conventional surfactants are used.

As used herein, carrier means organic or inorganic, natural or synthetic material with which the active ingredient is combined to facilitate its application to plants, seeds or 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, chlorinated 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, phenolsulfonic and naphthalenesulfonic acid salts, ethylene oxide polycondensates with fatty alcohols, fatty acids or fatty series amines, substituted phenols (especially alkylphenols or arylphenols), sulfosuccinic acid ester salts, taurine derivatives ( especially alkyltaurates) and phosphoric acid esters with alcohols or condensation products of ethylene oxide with phenols. The presence of at least one surfactant is of general importance when the active ingredient and / or the inert carrier are insoluble in water, the water being the basic carrier medium for the dosage form.

Thus, for application purposes, the compounds of the invention and combinations of the invention are generally used in the form of compositions of the invention. These compositions may take very different solid or liquid forms.

Solid forms of the compositions of the present invention include powder formulations for application

CS 266 339 B2 by dusting or throwing (in which the active substance concentration can be up to 100%) and granules, in particular granules produced by extrusion, compression, impregnation of a granular carrier or granulation of powders (active substance content of these granules in the latter cases) between 1 and 80%).

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

These compositions may also contain all kinds of other excipients, such as protective colloids, adhesives, thixotropic agents, penetrating agents, stabilizers, complexing agents and the like, as well as other known active substances with pesticidal properties (in particular insecticides or fungicides), auxiliary agents plant growth (especially fertilizers) or substances acting as plant growth regulators. In general, the compounds of the present invention may be combined with all solid or liquid additives, as is conventional techniques used in the production of similar compositions.

The dosage employed when administering the compounds and combinations of the invention as fungicides ^; may vary within wide limits and depends in particular on the extent and severity of the fungal attack and the weather conditions.

Compositions containing 0.5 to 5,000 ppm of active ingredient are generally considered to be very suitable. These values apply to devices suitable for direct application. The range of 0.5 to 5,000 ppm corresponds to the range of 5x10 ⁵ to 0.5% by weight.

More preferably, the compositions for storage and transport contain from 0.5 to 95% by weight of the active ingredient.

Thus, the compositions of the present invention suitable for use in agriculture may contain the active compounds of the present invention over a wide concentration range ranging from 5x10 ^-5 to 95% by weight.

In general, the compositions of the invention generally contain from about 0.05 to 95% by weight of the active compounds of the invention (compound of formula I and Group II), about 1 to 95% of one or more solid or liquid carriers, and optionally 0.1 to 95%. Preferably about 5 to 40% of one or more surfactants.

Emulsifiable or soluble concentrates most often contain 10 to 80% active ingredient, while emulsions or solutions suitable for direct application contain 0.01 to 20% active ingredient. In addition to the solvent, the emulsifiable concentrates may contain, if desired, 2 to 20% of suitable additives, such as the aforementioned stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives.

. The following are examples of compositions of several concentrates.

Example F1 Example F2

active substance 400 g / liter active substance 250 g dodecylbenzenesulfonate 24 g / liter epoxidized vegetable oil. 25 G alkali metal a mixture of alkylarylsulfonates, fatty condensation product of nonylphenol 16 g / liter alcohols and polyglycol ether 100 ALIGN! G with 10 moles of ethylene oxide 200 g / liter dimethylformamide 50 G cyclohexanone xylene 575 G aromatic solvent to 1 liter * '

Using these concentrates, emulsions of any desired concentration can be obtained after dilution with water, which are particularly suitable for foliar application.

CS 266 339 B2

Suspension concentrates, which can also be applied by spraying, are prepared so as to form a stable, non-depositing liquid product and usually contain an o | 10 to 75% of active ingredient, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents and from 0 to 10% of suitable additives such as antifoam, corrosion inhibitors, stabilizers, penetration 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. Organic solids or inorganic salts may be dissolved in the carrier, which additives serve to help prevent sedimentation or act as antifreeze agents.

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

Examples of compositions are the following wettable powders. Example F3 ‘ active substance 50 % calcium lignosulfonate (deflocculating agent) 5 % Isopropyl naphthalenesulfonate (anionic surfactant) 1 % non-caking silica 5 % kaolin (filler) 39 %

Example F4

70% wettable powder active substance 700 G sodium dibutylnaphthalenesulfonate 50 G the product of the condensation of naphthalenesulfonic acid phenolsulfonic acid and formaldehyde in a ratio 3: 2: 1 30 G kaolin 100 ALIGN! G chalk (Champagne) 120 G

Example F5

40% wettable powder active substance 400 G sodium lignosulfonate 50 G sodium dibutalnaphthalenesulfonate 10 G silica 540 G

Example F6

25% wettable powder active ingredient 250 g sodium lignosulfonate45 g mixture of equal parts by weight of chalk (Champagne) and hydroxyethylcellulose 19g sodium dibutylnaphthalenesulfonate 15g silica 195g chalk (Champagne) 195g kaolin 281g

CS 266 339 B2

Example F 7

25% wettable powder active substance 250 G isooctylphenoxy-polyoxyethylenethanol 25 G a mixture of equal parts by weight of chalk (Champagne) and hydroxyethyl cellulose 17 G sodium aluminosilicate 543 G kieselguhr 165 G : к 1 a d F 7 10% wettable powder active substance 100 ALIGN! G a mixture of sodium salts of saturated fatty acid sulphates 30 G the product of the condensation of naphthalenesulfonic acid with formaldehyde 50 G kaolin 820 G

To produce these wettable (or sprayable) powders, the active ingredients are thoroughly mixed in a suitable mixer with the other ingredients, and the mixture is ground in a mill or other suitable holding device. In this way, spray powders having a preferred wettability and suspendability are obtained, which can be suspended at any desired concentration in water and the resulting suspension can be used very advantageously, in particular for application to plant leaves.

Pastes can be produced instead of wettable powders. The conditions and methods of making and using these pastes are analogous to those described for wettable or sprayable powders.

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

Granules intended for application to soil are usually prepared so that their size is between 0.1 and 2 mm. These granular compositions may be prepared by agglomeration or impregnation. Generally, the granules contain 0.5 to 25% of active ingredient and 0 to 10% of additives such as stabilizers, release retardants, binders and solvents.

The composition of the following granulate is exemplified.

Example F9 active ingredient 50 g epichlorohydrin 2.5 g polyglycol cetyl ether 2.5 g polyethylene glycol 35 g kaolin (particle size 0.3 to

0.8 mm) 910 g

In this particular case, the active ingredient is mixed with epichlorohydrin, dissolved in 60 g of acetone, and polyethylene glycol and polyglycol cetyl ether are added to the solution. The resulting solution was sprayed with kaolin and the acetone was evaporated in vacuo. Microgranules of this kind are preferably used to combat soil fungi.

CS 266 339 B2

The compounds of the invention and combinations thereof may also be used in the form of dusts.

For example, a composition consisting of 50 g of active ingredient and 950 g of talc or a composition of 20 g of active ingredient, 10 g of finely divided silica, and

970 g talc. The above ingredients are mixed, comminuted and applied by dusting.

The invention is illustrated by the following non-limiting examples.

Examples 1 to 3 illustrate specific methods for preparing compounds of the invention. These compounds are characterized by physical properties, including, among other things, the shift values of the -O-CH-O- (acetal moiety) in the NMR spectrum in delta values. These shifts are measured in ppm and are relative to tetramethylsilane as the reference substance. These NMR spectra are measured at 100 MHz in deuterochloroform.

Examples 4 to 10 illustrate the fungicidal properties of the compounds of the invention and their application.

^ Example 1

The product of formula V is prepared

Cl-

_CH2 --N - N

(IN)

According to the procedure described in European Patent Application No. 151 084, 40 ml of trifluoroethanol are mixed with 10.7 g of the product of formula V and hydrogen chloride gas is added until the weight gain is 1.39 g. The reaction mixture is heated at 70 ° for 2 hours. C, then poured into 500 ml of water containing 10 g of sodium carbonate and extracted with ethyl acetate. The organic solution was washed with water, dried and evaporated after filtration. 8 g of crystalline product are obtained consisting of a mixture of two diastereomers of the compound of formula I. This product melts at 80 ° C with heating and its NMR spectrum contains a shift at 5.18 and 5.41 ppm.

Example 2 '

The product prepared according to Example 1 was subjected to liquid chromatography on a silica gel column at a pressure of 0.03 MPa using a mixture of ethyl acetate and heptane (80:20 by volume) as eluent.

The first fraction A (3 g) and the second fraction V (3.6 g) were collected.

Each of these fractions forms a crystalline precipitate. Crystals A obtained from fraction A correspond to one of the diastereomers. These crystals melt at 84 ° C and in their NMR spectrum the proton shift at delta 5.41 ppm. Diastereomer A is characterized in that it contains a triazolylmethyl group and a trifluoroethoxy group on the same side of the plane of the tetrahydrofuran ring.

Crystals V obtained from fraction V correspond to the second diastereomer. These crystals melt at 167 ° C and in their NMR spectrum the proton shift at delta is 5.18 ppm.

Example 3 3 ml of trifluoroethanol are mixed with 10.8 g of the product of formula

CS 266 339 B2

ОН

prepared according to the procedure of European Patent Application No. 151 084.

Hydrogen chloride gas was added to obtain a weight gain of 1.5 g, the reaction mixture was heated at 70 ° C for 4 hours, then poured into 500 ml of water containing 10 g of sodium carbonate and extracted with chloroform. The organic phase is washed with water and, after drying, evaporated. 12.7 g of product of formula I are obtained in the form of a mixture of two diastereomers.

Example 4

The experiment is carried out on four plots in the wild. On each plot there are 4 with apple trees of the variety Calville, which are highly sensitive to scab (Venturia inaequalis). The treatment is carried out at 12-day intervals ranging from flowering to the middle phase of fruit growth. The treatment consists of applying a spray mixture, i.e. a dilute aqueous emulsion of the active ingredient described in Example 1. This spray mixture, which is applied at a rate of 1000 liters / ha, is prepared by diluting the emulsifiable concentrate to an active substance concentration of 2.5 g / 100 liters. . The emulsifiable concentrate used contains 62 g / liter of active ingredient, 203 g / liter of cyclohexanone, 609 g / liter of acetophenone, 50 g / liter of calcium alkylarylsulfonate and 100 g / liter of castor oil ethylene oxide condensation product.

The results obtained are compared with those obtained using a related product, i.e. the compound of Example 42 of European Patent Application Publication No. 151,084, which is closest chemically to the substance of the invention. It is 1-C2- (2,4-dichlorophenyl) -4-methyl-5- (2,2,2-trifluoroethoxy) tetrahydrofuran-2-ylmethyl-1H-1,2,4-triazole corresponding to the formula

Tr

is a triazole residue.

This product is referred to below as a reference. The above-mentioned comparative substance, as well as the compound of Example 1 according to the invention, includes all possible diastereomeric forms.

The results of the experiment are measured and expressed as follows:

phytotoxicity, which is measured 1 day after the third treatment, is expressed as a percentage after visual assessment of the general condition of the leaves and fruits; a value of 15% shall be considered as the maximum permissible value;

foliar efficacy is measured 1 day after the fifth treatment and is expressed as the percentage of scab infestated in percentage;

«Effect on fruit is measured after the end of the treatment and is expressed as the percentage of fruit affected.

The results are summarized as follows:

CS 266 339 B2

active substance phytotoxicity Effect on leaves Effect on fruits the product of Example 1 1 32.2 4.4 comparative substance 1 80.0 58.7 untreated (control) 0 99.8 84.2

^ í í к 1 and d 5

The same method is used as in Example 4 except that apple trees of the Golden variety are treated with a spray mixture containing the active ingredient in a concentration of 5 g / 100 liters.

The results are summarized as follows:

active substance phytotoxicity Effect on leaves Effect on fruits the product of Example 1 0 3 0 comparative substance 0 39.8 5.9 untreated (control) 0 99.7 87

Example 6

The experiment was carried out on 4 plots in the wild. On each of these plots 15 vines of the Carignan variety, which are highly sensitive to powdery mildew (Uncinula necator), are grown. The treatment is carried out at fortnightly intervals from budding to ripening (the period when the grapes change color).

The above treatments consisted of applying the same spray mixture as in Example 4 at a concentration of 1.5 g of active ingredient per 100 liters.

The results obtained, which are evaluated as in Example 4, are summarized as follows:

Active ingredient phytotoxicity (measured on day 13 after the second treatment) Effect on leaves (measured on day 8 after the 3rd treatment) Product of Example 1 Comparative substance

23.5

29.5 efficacy on fruits (measured on day 14 after treatment) untreated (control)

100 ALIGN!

96.2

Examples 7 to 10

The experiment was carried out on 4 plots (10 m) in a test field sown with wheat. One or two treatments are carried out at the time the first signs of the disease appear on the plots.

The same spray mixture as in Example 4 was used for the treatment, but applied in an amount corresponding to a dose of 90, 120 or 150 g / ha (depending on the test).

No signs of phytotoxicity were observed in all these tests.

CS 266 339 B2

In Example 7, a Nebraska wheat crop infected with Puccinia striiformis is treated. The results are evaluated 10 days after the second treatment on the highest leaf just below the ear.

In Example 8, a Vaillant wheat culture treated with wheat rust (Puccinia recondita) is treated. Results are evaluated 19 days after the first treatment on the highest leaf below the ear.

In Example 9, a culture of wheat of the Longbow variety, attacked by Septoria tritici, is treated. Results are evaluated 46 days after treatment (single treatment) on the highest leaf below the ear. .

In Example 10, a wheat culture of the Roazon variety is treated. The results are evaluated 44 days after treatment (single treatment) on the second leaf from the cob down (the first leaf - the highest leaf - is not affected by the disease). This measurement illustrates the good stability of the active ingredients.

The results of the experiments are measured and evaluated as follows:

foliar efficacy: percentage of leaves infected with disease;

leaf surface activity: the percentage of leaf surface affected by the disease.

The results are summarized as follows:

active substance rate (g / ha) Example 7 Effect on leaves Example 8 Example 9 Effect on leaf surface Example 10 Effect on leaf surface Effect on leaves efficiency on leaf surface product from 90 4.6 75 2.8 3.6 21.6 of Example 1 120 2.1 36 0.8 2.6 10.3 150 1,2 28 0.6 2.9 3.9 comparative 90 39.2 88 8.8 6.9 10.9 substance 120 27.3 93 5.4 7.7 11.7 150 19.5 74 4.7 4.8 15.9 untreated (control) 0 80 100 ALIGN! 27.2 21.4 58.7

Example 11

In vivo efficacy test for Erysiphe graminis sp. hordei on barley (powdery mildew) «·.

By gently grinding the ingredients below, an aqueous emulsion of the active compound to be tested is prepared.

active substance tested Tween 80 (surfactant consisting of oleate of the condensation product of ethylene oxide with sorbitan) diluted with water to a concentration of 10% water 90 mg 0.45 ml 90 ml

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

Barley is sewn into pots filled with clay soil and, after emergence, 10 cm high plants are sprayed with an aqueous emulsion of the test substance at the concentration indicated below. The test is repeated twice. After 24 hours, barley plants are dusted with spores of Erysiphe graminis using plants infected with the disease. The experiment is evaluated 8 to 12 days after the infestation;

CS 266 339 B2

Tests performed under the above conditions showed the following results:

Use of the product of Example 1 and Compound A of Example 2 at a concentration of 0.1 g / liter ensures complete protection of the plants from infection (protection greater than or equal to 95%).

Example 12 <

In vivo efficacy test for Puccinia recondita on wheat

Wheat plants grown in pots filled with clay soil are treated by spraying with aqueous emulsions of the same composition as in Example 11 containing the active ingredient at different concentrations after reaching a height of 10 cm. The test is repeated twice for each concentration.

After 24 hours, wheat plants were sprayed with an aqueous spore suspension of Puccinia recondita (50,000 spores / ml) prepared using infested plants. The plant pots are then transferred to an incubation chamber at about 18 ° C and 100% relative humidity for 48 hours.

** y. ,

After these 2 days, the relative humidity in the chamber is reduced to 608. The condition of the treated plants is evaluated between 11 and 15 days after infestation compared to untreated control plants.

In the test performed under the above conditions, the following results were found:

At a concentration of 0.1 g / liter, the compounds of Examples 1 and 2 (Compound A) provide complete protection against the above fungus.

Example 13

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

The activity of the compounds according to the invention on the following fungal species responsible for secondary cereal diseases is investigated:

Pseudocercosporella herpotrichoides Helminthosporium gramineum Botrytis cinerea (Gray mold)

Pyrenophora aveпае (Brown oatspot) Septoria nodorum Helminthosporium teres (Brown barnspot)

Abbreviations in brackets will be used to identify each mushroom in the table below ·

Each test is performed as follows:

Potato, glucose and agar medium (PDA medium) is sterilized in a series of Petri dishes (20 ml per 'each dish) after sterilization in a lava flow at 120 ° C in a highly supercooled state. '

After the dishes are filled, an acetone solution of the test compound is injected into the subcooled medium to achieve the desired final concentration.

The same Petri dishes are used as controls as in the experiment, containing the same amount of culture medium but without the active ingredient.

(CERC);

(HELM G).

(BOT) (PYRE) I (SEPT N) I. i

(HELM T)

CS 266 339 B2

After 24 or 48 hours, each dish is inoculated with a fragment of mycelium obtained by previous cultivation of the respective fungus.

The plates are stored at 22 ° C for 2 to 10 days (depending on the test sponge), after which the growth of the fungus in the drug-containing plates is compared with that of the control plates.

In this way, the lowest dose at which the compound inhibits the development of the respective fungus by 80-100% is found for each test compound. This dose is referred to as the minimum. inhibitory concentration.

The above-mentioned minimum inhibitory concentrations (in ppm) are summarized in the following table, in which the test fungi are referred to by the abbreviations above.

Ми

Table

The compound of Example no.

Minimum inhibitory dose (ppm ie mg / liter)

CERC HELM G HELM T PYRE SEPT (B) 10 30

3 100

100 30 30

30 30

The concentrations of the active compound suspensions used in the previous examples are given in g / liter and essentially correspond to the same application rates in g / ha.

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

Example 14.

In vitro potency test for Septoria nodorum (compound II - iprodione)

A series of sterile Petri dishes was charged with a strongly supercooled culture medium.

Upon filling, an acetone solution of the active ingredient formed by combining the compound prepared in Example 1 with iprodione is injected into the subcooled environment. Combinations with different proportions of components are used and the acetone solution is dosed in an amount to achieve the desired concentration of active ingredient. .

The same Petri dishes filled in the same way are used as controls, with no active ingredient in the nutrient medium.

After 24 hours, each dish is inoculated with a piece of fungal mycelium from a previous cultivation of the fungus. ’

The plates are stored at 22 + 2 ° C for 15 days, after which the growth of the fungus in the plates containing the active ingredient is compared to that of the fungus in the control plates.

The percentage inhibition is calculated using the following formula:

T - d where ¹

I% inhibition

CS 266 339 B2

T = mean value of the diameter of the mycelium target in the control dish (mm)

TT = mean diameter of the mycelium target grown in the treated dish d = diameter of the mycelium fragment used at the start of the vaccination test

In tests carried out under the conditions described above, the following values of actual inhibition of fungal development in% were found.

Inhibition of Septoria nodorum development in%

Iprodion in active substance according to (mg / liter) \ invention (mg / liter) 0 0.3 3 0 0 43 69 3 70 85 95 10 83 90 100 ALIGN!

Example 15

In vitro potency test for Septoria nodorum (compound II - fenpropimorph)

The procedure is the same as in the previous example. The following% inhibition of Septoria nodorum was found;

Fenpropimorph (mg / liter) Active substance according to N. invention (mg / liter) 0 1 3 0 0 62 69 1 76 90 94 2 83 93 98

Example 16

In vitro potency test for Septoria nodorum (compound II - tridemorph)

The procedure is the same as in the previous example. The following% inhibition values of Septoria nodorum were found;

Tridemorph (mg / liter) n active ingredient according to the invention (mg / liter) * 0 0.3 1 0 0 43 62 0.3 72 82 .90 3 90 95 96 : к 1 and d 17

In vitro potency test on Septoria tritici (Wheatgrass) (Compound II-Captafol)

The process was carried out under the same conditions as in the previous example. The following% inhibition values of Septoria tritici were found;

CS 266 339 B2

.Captafol \ (mg / liter) active ingredient according to the invention (mg / liter) 0 3 - 0 0 35 100 ALIGN! 84 92 300 100 ALIGN! 100 ALIGN!

Example 18

In vitro potency test for Botrytis cinerea (gray mold) (compound II - carbendazim)

The process was carried out under the same conditions as in the previous example. The following inhibition values of Botrytis cinerea in% were found;

Carbendazim \ active ingredient according to (mg / liter) of the invention (mg / liter) 010

035

0,08 7285

Example 19

In vitro potency test for Botrytis cinerea (gray mold) (compound II - captan)

The process was carried out under the same conditions as in the previous example. The following inhibition values of Botrytis cinerea in% were found;

Captan k active ingredient according to (mg / liter) X of the invention (mg / liter) 010

035

986

Example 20

In vitro potency test for Botrytis cinerea VE 35 (gray mold) (compound II - iprodione)

The process was carried out under the same conditions as in the previous example. The following inhibition values of Botrytis cinerea VE 35 v

Active substance according to (mg / liter) of the invention (mg / liter).

088

390

Example 21

In vitro potency test for Alternaria tenuis (compound II - iprodione)

The process was carried out under the same conditions as in the previous example. The following inhibition values of Alternaria tenuis in% were found;

CS 266 339 B2

Iprodion \ (mg / liter) active ingredient according to the invention (mg / liter) 0 10 0 0 68 10 90 100 ALIGN!

Example 22

In vitro potency test for Monilia laxa (stone fruit monillosis) (compound II - carbendazim)

The process was carried out under the same conditions as in the previous example. The following% inhibition values of Monilia laxa were found:

Carbendazimy active ingredient according to

(mg / liter) Of the invention (mg / liter) 0 0.3 1 0 0 31 77 0.008 76 86 100 ALIGN! 0.015 92 92 95

Example 23

In vitro potency test for Helminthosporium gramineum (barley stiffness) (compound II - fenpropimorph) ·

The process was carried out under the same conditions as in the previous example. The following% inhibition values of helminthosporium gramineum were found:

Fenpropimorph \ active ingredient according to (mg / liter) \ of the invention (mg / liter) 0 10. 30 0 0 65 75 0.1 0.00 78 69 0.3 0.00 52 75

Example 24

In vitro potency test for Fusarium roseum (fusariosis) (compound II - chlorothalonil)

The process was carried out under the same conditions as in the previous example. The following% inhibition values of Fusarium roseum were found;

Chlorothalonil \ (mg / liter) active ingredient according to the invention (mg / liter) 0 0.3 30 0 0 56 49 100 ALIGN! 51 51 75 300 73 74 83

Example 25

In vitro potency test for Fusarium roseum (fusariosis) (compound II - maneb)

The process was carried out under the same conditions as in the previous example. The following% inhibition values of Fusarium roseum were found;

CS 266 339 B2

Maneb \ (mg / liter) ¹ active ingredient according to the invention (mg / liter) 0 0.3 30 0 0 6 49 30 75 83 85 50 73 78 83

Example 26

In vitro potency test for Venturia pirina (pear scab) (compound II - captan)

The process was carried out under the same conditions as in the previous example. The following% inhibition values of Venturia pirina were found:

Captan (mg / liter) active ingredient according to the invention (mg / liter) 0 10 100 ALIGN! 0 0 70 94 30 46 78 95 100 ALIGN! 62 88 95

Example 27

In vitro potency test for Pseudocercosporella herpotrichoides (compound II - tridemorph)

The process was carried out under the same conditions as in the previous example. The following inhibition values of Pseudocercosporella herpotrichoides were found.

Tridemorph active substance according to

(mg / liter) of the invention (mg / liter) 0 0.3 3 0 0 22nd 77 0.3 18 41 80 1 52 64 91 3 86 86 96

Example 28

In vitro potency test for Erysiphe graminis f. Sp. Hordei on barley (powdery mildew)

The experiment was carried out in the same manner as in Example 11 except that the active ingredient used was a combination of the compound of Example 1 with tridemorph in a 1: 1 weight ratio.

Full protection (greater than 95%) is achieved when this combination is applied at a concentration of 0.06 g / liter.

Example 29

In vivo efficacy test for Botrytis cinerea (mold) on tomatoes

An aqueous emulsion was prepared as described in Example 11. The active ingredient used is a combination of the compound obtained according to Example 1 and iprodione in a 1: 1 weight ratio.

CS 266 339 B2

Tomato plants (Marmande variety) grown in a greenhouse are treated with an aqueous emulsion prepared above from 30 to 40 days old.

After 24 or 48 hours, the leaves are cut from the treated plants and placed in the leaves

Petri dishes with a diameter of 11 cm, on the bottom of which is moistened circular filter paper. Place 5 leaves in each dish.

Inoculation is carried out with a syringe in which 3 drops of a spore suspension of the fungus Botrytis cinerea are applied to each leaf. This suspension is obtained from a 15-day culture of the above fungus which is suspended in a nutrient solution (80,000 units / ml).

Six days after contamination, the experiment is evaluated by comparison with the condition in the untreated control.

The above combination of active ingredients provides complete (greater than 95%) protection against fungus when applied at a concentration of 0.66 g / liter.

Example 30

In vivo efficacy test for Erysiphe graminis f. Sp. hordei on wheat (powdery mildew)

The active ingredient is prepared in the same manner as in Example 11, except that the compound prepared according to Example 11 is combined with tridemorph and fenpropimorph in a weight ratio: the compound of the example lithridemorph or fenpropimorph = 1.1.

Wheat plants grown in pots filled with clay soil are treated by spraying with an aqueous emulsion of the active ingredient at the concentration indicated below after reaching a height of 10 cm. The test is repeated twice. After 24 hours, the wheat plants are dusted with spores of Erysiphe graminis using infested plants.

The experiment is evaluated 8 to 12 days after contamination.

Working under the conditions described above, it has been found that the active compound combination tested at 0.063 g / liter provides complete protection (greater than or equal to 95%) against fungal attack. '

Example 31

In vivo efficacy test against Septoria nodorum

The active ingredient is prepared in the same manner as in Example 11 except that the active ingredient is a combination of the compound prepared according to Example 1 with iprodione in a 1: 1 weight ratio.

Wheat plants grown in pots filled with clay soil are treated by spraying with an aqueous emulsion of the active ingredient at the concentration indicated below after reaching a height of 10 cm. The test is repeated twice.

After 24 hours, treated wheat plants are sprayed with an aqueous spore suspension (150,000 spores / ml) obtained from in vitro cultured fungus cultures. The pots of wheat plants are then stored in an incubation chamber at about 20 ° C and 100% relative humidity for 8 days. Between 8 and 15 days after contamination, the condition of the test plants is evaluated by comparison with untreated control plants.

Working under the conditions described above, it has been found that the above combination is effective

CS 266 339 B2 substances applied in concentration. 0.25 g / liter provides greater than 90% protection against said sponge.

Example 32

In vivo preventive activity test against Monilia sp. and Penicillium sp., which causes fruit rot, especially apples

The two tests, although independent of each other, are summarized in one example because they are performed in the same manner. The procedure was as in Example 11 except that the active ingredient used was the combination of the compound prepared according to Example 1 with iprodione in a 1: 1 weight ratio.

Apples are sprayed with an aqueous suspension of the active ingredient concentration indicated below. The test is repeated twice.

After 24 hours, treated apples are sprayed with an aqueous suspension of spores of the test fungus (50,000 spores / ml for Monilia sp. And 250,000 spores / ml for Penicillium sp.), Obtained from infested fruits. The apples are then placed in an incubation chamber at a temperature of 20 ° C and 90 to 100% relative humidity. Between 5 and 10 days after contamination, the condition of the test fruit is evaluated by comparison with untreated control fruit.

Working under the conditions described above, it has been found that the aforementioned combination of active ingredients, when applied at a concentration of 0.66 g / liter, gives Monilia sp. protection of 49% and, in the case of Penicillium sp. of 21%.

Example 33

In vivo efficacy test for Erysiphe graminis f. Sp. hordei on barley (powdery mildew)

The procedure is the same as in Example 11 except that a combination of the compound prepared according to Example 1 and tridemorph is used as the active ingredient in a weight ratio: the compound of Example Litridemorph = 0.033.

Barley plants grown in pots filled with clay soil are sprayed with an aqueous emulsion at the concentrations of the active ingredient indicated after reaching a height of 10 cm. The test is repeated twice. After 24 hours, barley plants are dusted with spores of Erysiphe graminis using infested plants.

The experiment is evaluated 8 to 12 days after contamination.

When working under the conditions described above, the aforementioned combination of active ingredients applied at a concentration of 0.1 g / liter provides 50% protection against fungus.

Example 34

In vivo efficacy test on grapevine peronospore (Plasmopara viticola)

An aqueous emulsion of the active ingredient formed by combining the compound of Example 1 with phosetyl-Al in a weight ratio of 0.5 was prepared in the same manner as in Example 11.

Vine cuttings (Vitis vinifera, Chardonnay variety) are planted in pots for further cultivation. After 2 months (8-10 leaf stage, 20-30 cm height) plants are sprayed with an aqueous suspension or solution of the test substance. Each plant is treated with about 5 ml of the test composition.

.. 'fate'. . .7

CS 266 339 B2

The plants are allowed to dry for 24 hours and then sprayed with an aqueous spore suspension

Plasmopara viticola (vine peronospore) in an amount of about 1 ml / plant (i.e., about 5 spores / plant).

After this contamination, the vine plants were placed in an incubation chamber at 18 ° C and an atmosphere saturated with humidity for 2 days and then stored at 20-22 ° C for a further 5 days at 90-100% relative humidity.

The experiment is evaluated 7 days after contamination.

Working under the conditions described above, it has been found that the aforementioned combination of active ingredients applied at a concentration of 3 g / liter provides complete protection against peronospore.

Claims (4)

A fungicidal composition, characterized in that it contains a compound as an active ingredient Xvzorce I CH ₂ -N-N v (I) or a salt thereof, in combination with at least one agriculturally acceptable inert carrier. 2. A composition according to claim 1, wherein the active ingredient is a compound of the above formula (I) in the form of a mixture of diastereomers. 3. A composition according to claim 1, wherein the active ingredient is a compound of the above formula (I) in the form of diastereomers wherein the triazolylmethyl group and the trifluoroethoxy group are on the same side of the plane of the tetrahydrofuran ring. 4. A method for producing an active substance of the formula I according to claim 1, characterized in that trifluoroethanol formula _{CF3 CH2} OH is in the presence of an acidic catalyst with a compound of formula IV / 'OHOR3 I I I3 Cl - σ C - CH _{2 -} CH _{2 -} CH - OR ^J CH ₂ -N-N (IV) in which is C 1 -C 4 alkyl, or both together form C 2 or C 3 alkylene.