NO167459B - TRIAZOLIC COMPOUNDS, THEIR USE AS FUNGICIDES, AND AGENTS FOR MONITORING OF SUBSTANCES IN CROPS. - Google Patents

Description

The present invention relates to triazole compounds, and the peculiarity of the compounds according to the invention is that they have the general formula

in which

Hal is a halogen atom,

Y is a halogen atom and X^ represents a halogen atom, hydroxy, lower alkoxy, lower alkylthio, phenoxycarbonyloxy, chlorolower alkylthio, oxo or methoxyimino.

The invention also relates to the use of the aforementioned compounds as fungicides, and the invention also relates to an agent for controlling fungal diseases in crops, and the peculiarity of the agent according to the invention is that it contains as active substance 0.5 - 95% by weight of a triazole compound as stated in claim 1 or 2 in addition to an inert carrier.

These and other features of the invention appear in the patent claims.

Numerous products, especially fungicides, containing triazole groups are already known, especially from European patent application 151,084.

An aim of the present invention is to provide compounds with improved properties in the treatment of fungal diseases, in particular an improved spectrum of use.

In the present context, it is understood that the term "lower", when it denotes an organic radical, means that the radical contains no more than 6 carbon atoms. The radical can be straight chain or branched.

The compounds with formulas I and the compounds which can advantageously be used as starting compounds in the production processes, and which will be described in connection with the description of these processes, can exist in one or more isomeric forms depending on the number of asymmetric centers in the molecule. The invention therefore relates to all optical isomers as well as their racemic mixtures and the corresponding diastereoisomers. The separation of the diastereoisomers and/or the optical isomers can be carried out using methods known per se.

The compound according to the invention can be used for preventive as well as curative control of fungi, especially of the type basidiomycetes, ascomycetes, adelomycetes or fungi imperfecti, especially rust fungi, molds, cercosporella diseases, fusarium diseases, helmintosporium diseases, septoria diseases and rhizoctonia diseases on crops and plants in general and especially cereals such as wheat, barley, rye, oats and their hybrids and also rice and maize. The compounds according to the invention are active in particular against fungi, especially of the type basidiomycetes, ascomycetes, adelomycetes and 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, Whetzelinia scclerotiorum, Monilia laxa, Mycosphaerella fijiensis, Marssonina panettoniana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzia sp., Phialophora cinerescens, Phoma betae , Phoma foveata, Phoma Hungary, Ustilago maydis, Verti-cillium dahliae, Ascochyta pisi, Guignardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia sclerotiorum, Sclerotinia minor, Coryneum cardinale and Rhizoctonia solani.

They are also and continue to be active against the following fungi: Acrostalagmus koningi, Alternaria, Colletotrlchum, Corticium rolfsii, Diplodia natalensis, Geaumannomyces graminis, Gibberella fujikuroi, Hormodendron cladosporioides, Lentinus degener or tigrinus, Lenzites quercina, Memnonielle echinata, Myrothecium verrucaria, Paecylomyces varioti , Pellicularia sasakii, Phellinus megaloporus, Polystictus sanguineus, Poria caporaria, Sclerotium rolfsii, Stachybotris atra, Stereum, Stilbum sp., Trametes trabea, Trichoderma pseudokoningi and Trichothecium roseum.

The compounds according to the invention are of particular interest because of their broad spectrum with respect to grain diseases (downy mildew, rust, eyespot, net blotch, leaf spot and foot rot). They are also of particular interest due to their effectiveness against gray mold "Botrytis) and cercospora diseases and because of this they can be added to crops as diverse as grapes, vegetables and trees and tropical crops such as peanut, banana, coffee, pecans and others.

In addition to the applications already described, the products in accordance with the invention also have an excellent biocidal effect against many other types of micro-organisms, among which fungi such as e.g. those belonging to the genera:

Pullularia such as e.g. species P. pullulans,

Chaetomium as e.g. species C. globosum,

Aspergillus such as e.g. species Aspergillus niger, Coniophora such as e.g. species C. puteana.

Due to their biological action, the products according to the invention make it possible to effectively control microorganisms whose reproduction causes numerous problems in agriculture and industry. For this reason, they are particularly well suited for the protection of plants or industrial products such as wood, leather, paints, paper, ropes, plastic materials and industrial water circuits.

They are particularly well suited for the protection of lignocellulosic products and especially of wood, regardless of whether this consists of wood for furniture or building materials, or wood that is exposed to climatic stresses such as e.g. wood for fencing, grape poles or railway sleepers.

The compound in accordance with the invention, used alone or in the form of mixtures as defined above when treating wood, is generally used with organic solvents and can be used as necessary in combination with one or more known biocidal products such as . pentachlorophenol, metal salts, especially salts of copper, manganese, cobalt, chromium or zinc derived from inorganic or carboxylic acids (heptanoic acid, octanoic acid or naphthalene acid), organic tin-mercaptobenzothiazole complexes, insecticides such as pyrethroids or organochlorine compounds.

Finally, the compounds have an excellent selectivity with respect to crops.

They are advantageously applied in doses of 0.005 to 5 kg/ha and more specifically 0.01 to 0.5 kg/ha.

In practical use, the compound according to the invention is rarely used alone. Most often they form part of mixtures.

These mixtures, which can be used for the protection of plants against fungal diseases, or in plant growth-regulating mixtures, contain as the active substance a compound in accordance with the invention as described above, in association with solid or liquid carriers which are tolerable within agriculture, and/or surfactants that are also tolerable in agriculture. Conventional inert carriers and in conventional surfactants can especially be used.

The term "carrier" in the present description denotes a natural or synthetic organic or inorganic material with which the active substance is combined to facilitate its application to the plant, to the seeds or to the ground. This carrier is therefore generally inert and must be tolerable in agriculture, especially on the treating plant. The carrier can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.).

The surfactant can be an emulsifier, dispersant or wetting agent of ionic or non-ionic type. Examples include polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic acid salts or naphthalene-sulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols or arylphenols), sulforaic acid ester salts, taurine derivatives (especially alkyl taurates), phosphoric acid esters of alcohols or of polycondensates of ethylene oxide with phenols. The presence of at least one surface-active agent is generally necessary when the active substance and/or the inert carrier is insoluble in water and the vector agent for the application is water.

For their use, the compounds of formula (I) are generally in the form of mixtures and these mixtures according to the invention are themselves in various solid or liquid forms.

Solid mixture forms that can be mentioned are powders for atomization or dispersion (with a content of compound of formula (I) up to 100%) and pellets, in particular those obtained by extrusion, by compaction, by impregnation of a granulated carrier, or by granulation starting from a powder (the content of compound of formula (I) in these pellets is between 1 and 80% in the latter cases).

Solutions, especially water-soluble concentrates, emulsifiable concentrates, emulsions, trickle-able preparations, aerosols, wettable powders (or powders for spraying) and pastes can be mentioned as liquid mixture forms or forms which are to constitute liquid mixtures when they are applied.

The emulsifiable or soluble concentrates usually contain 10 to 80% active substance, while the emulsions or solutions ready for application contain 0.01 to 20% active substance.

These mixtures can also contain any other type of constituents such as e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, sequestering agents and the like, as well as other known active substances with pesticidal properties (especially insecticidal or fungicidal properties) or properties that promote plant growth (especially fertilizers) or plant growth regulating properties. More generally, the compound according to the invention can be combined with all the solid or liquid additives corresponding to the usual methods of composition.

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

In the case where the compound according to the invention is used as fungicide, the doses used can vary within wide limits, especially in accordance with the virulence of the fungi and the climatic conditions.

In general, mixtures containing 0.5 to 5000 ppm active substance are very suitable and these values apply to mixtures ready for application. Ppm stands for "parts per million". The range from 0.5 to 5000 ppm corresponds to a range of 5 x IO-<5> to 0.5% (weight percentages).

With regard to mixtures suitable for storage and transport, they may more advantageously contain from 0.5 to 95% by weight of active substance.

The mixtures according to the invention for use in agriculture can thus contain the active substance according to the invention within very wide limits, from 5 x 10_<5>% to 95 weight*.

As an example, the compositions of some concentrates are given below:

Example F (mixture) 1:

According to another composition for an emulsifiable concentrate, the following is used:

Example F 2:

From these concentrates, by diluting with water, it is possible to obtain emulsions of any desired concentration, which are particularly suitable for application to leaves.

Liquid preparations, which can also be applied by spraying, are prepared so that a stable liquid product is obtained that does not settle and usually contains from 10 to 75% active substance, from 0.5 to 15% surfactants, from 0.1 to 10% thixotropic agents and from 0 to 10% suitable additives such as antifoam agents, corrosion inhibitors, stabilizers, penetrant agents and adhesives, and as a carrier water or an organic liquid in which the active substance has little solubility or is insoluble. Certain solid organic substances or inorganic salts can be dissolved in the carrier to help prevent sedimentation, or as antifreeze agents for the water.

The wettable powders (or powders for spraying) are usually prepared so that they contain 20 to 95% active substance and they usually contain, in addition to the solid carrier, from 0 to 5% of a wetting agent, from 3 to 10% of a thickening agent and if necessary from 0 to 10% of one or more stabilizers and/or other additives such as penetrants, adhesives, or anti-caking agents, dyes, etc.

As an example shown in the following different compositions of wettable powders:

Example F 3:

Other compositions of powders for spraying, with 70% concentration, use the following ingredients:

Example F 4:

Another composition of powder for spraying, with 40% concentration, uses the following ingredients:

Example F 5:

Another composition of powder for spraying, with 25% concentration, uses the following ingredients:

Example F 6:

Another composition of powder for spraying, with 25% concentration, uses the following ingredients:

Example F 7:

Another composition of powder for spraying, with 10% concentration, uses the following ingredients:

Example F 8:

To obtain these powders for spraying or wettable powders, the active substances are intimately mixed in suitable mixers with additional substances, and the mixtures are ground in mills or other suitable grinding devices. The powder for spraying is obtained in this way with advantageous wettability and suspendability. They can be suspended in water at any desired concentration and these suspensions can be used very advantageously especially for application to plant leaves.

Instead of wettable powders, pastes can be prepared. The conditions and means of production and use of these pastes are similar to those for the wettable powders and powders for spraying.

As already indicated, the dispersions and the aqueous emulsions, e.g. mixtures obtained by diluting with water a wettable powder or an emulsifiable concentrate in accordance with the invention, included within the general framework of the present invention. The emulsions can be of the water-in-oil or oil-in-water type, and they can have a thick consistency similar to "mayonnaise".

Pellets for placement on the ground are usually produced so that they have a size between 0.1 and 2 mm and can be produced by agglomeration or impregnation. In general, the pellets contain 0.5 to 25% active substance and 0 to 10% additives such as stabilizers, slow release modifiers, binders and solvents.

According to an example of pellet composition, the following components are used:

Example F 9:

In this particular case, the active substance is mixed with epichlorohydrin and dissolved in 60 g of acetone. Polyethylene glycol and cetyl polyglycol ether are then added. The kaolin is moistened with the obtained solution and the acetone is then evaporated under vacuum. A micropellet of this type is advantageously used for the control of soil fungi.

The compounds of formula (I) can also be used in the form of powders for atomisation. A mixture containing 50 g of active substance and 950 g of talc can also be used. A mixture containing 20 g of active substance, 10 g of finely divided silica and 970 g of talc can also be used. The ingredients are mixed and ground and the mixture is applied by spraying.

The following examples illustrate special procedures for producing the compounds in accordance with the invention as well as the compounds themselves. The nomenclature for the compounds is given according to the French standard, with the exception that the numbering of the substituents is given before the substituents themselves.

Example 1 - Preparation of 1-(4-bromo-2-(2.4-dichlorophenyl)-tetrahydro-furan-2-ylmethyl)-1H-1.2.4-triazole.

Preconditions No. la. lb and let + lb

Step a)

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

An organomagnesium derivative is prepared by adding a solution of allyl bromide (110 ml) in ethyl ether (700 ml) and

tetrahydrofuran (200 ml) magnesium (110 g) during 3 hours at a temperature between 15 and 20°C. The mixture is boiled under reflux for 30 min. and decanted and the residue washed with ether.

A solution of alpha,2,4-trichloroacetophenone (175 g) in tetrahydrofuran (250 g) at -30°C is added to the organic phase and the mixture is neutralized with acetic acid. The mixture is washed with ether, dried over sodium sulphate, concentrated and then distilled under vacuum. A colorless oil (250 g) is obtained. Kp. (3 x 10_<2>mm Hg) = 140-142°C.

Step b)

Preparation of 1-(2-(2,4-dichlorophenyl)-2-hydroxypenten-4-yl)-1H-1,2,4-triazole

A mixture of the product obtained in step a) (106 g), triazole (55 g) and potassium carbonate (160 g) is heated in dimethylformamide (600 ml) at 120°C for 4 hours. Insoluble materials are filtered off and washed with dimethylformamide and the reaction mixture is concentrated under vacuum. The residue, dissolved in methylene chloride, is washed with water and then concentrated. The product is obtained by crystallization in ethyl acetate after dilution with heptane. A pale pink solid is isolated, m.p. 101°C (97 g).

Step c)

Preparation of Compounds Nos. 1a and 1b.

The compound obtained in step b) (35 g) in chloroform (200 ml) is treated with bromine at 0°C. After decolourisation, the solvent is evaporated and the residue is dissolved in methanol. An aqueous solution of potassium hydroxide is then added until a basic pH value is achieved. After evaporation of the medium under vacuum, the residue is extracted with ethyl acetate, washed with water and concentrated. The oil obtained (40 g) consists of a mixture of two diastereoisomers in essentially equal amounts. Using silica column chromatography, the least polar isomer No. 1a is isolated in sequence: white crystals m.p. 83°C and then the most polar isomer No. 1b: white crystals m.p. 94°C. After recrystallization, la is obtained with m.p. 96°C and lb with m.p. 104°C. The 50:50 mixture of la and lb has a m.p. 74°C.

The following compounds were prepared in the same manner using corresponding starting materials: 1-(4-bromo-2-(4-chlorophenyl)tetrahydrofuran-2-ylmethyl)-1H-1,2,4-triazole:

lc: m.p. 74°C, ld: m.p. 78°C and lc+d: m.p. 69°C.

Example II - Preparation of 1-(2-(2,4-dichlorophenyl)-4-hydroxytetrahydrofuran-2-methyl)-1H-1.2.4-triazole.

Compounds No. 2a and 2b

The isomer (10 g) from Example I, which is the least polar isomer, dissolved in chlorobenzene (30 ml) was refluxed for 48 hours in the presence of sodium benzoate (20 g) in water (30 ml) with the phase transfer catalyst "ADOGEN 464" methyltrialkylammonium chloride (lg).

After dilution with ether, the organic phase is washed with water and evaporated under vacuum. The residue is then treated with methanol (100 ml) in the presence of potassium hydroxide (7 g) at reflux temperature for 3 hours. The mixture is cooled, diluted with water and extracted with ethyl acetate and the product is washed to a neutral reaction and purified by means of chromatography, the crude product being obtained after concentration under vacuum. The alcohol 2a is isolated in the form of a white powder (2.8 g), m.p. 193°C.

By working in the same way, starting from the most polar isomer lb obtained according to Example I, the optically active alcohol 2b is obtained in the form of a white powder, m.p. 162°C. The 50:50 mixture of 2a and 2b is an oil.

Example III - Preparation of 1-(2-(2,4-dichlorophenyl)-4-ethoxytetrahydrofuran-2-ylmethyl)-1H-1,2,4-triazole.

Compounds No. 3a and 3b

The alcohol 2a (2.2 g) dissolved in dimethylsulfoxide (12 ml) is treated sequentially with 80% strength sodium hydride (0.42 g) and then with ethyl iodide (1.15 ml). After 15 min. medium is diluted with water and extracted with ethyl acetate. After washing with water, the solvent is evaporated and the residue is purified by silica column chromatography to give a colorless oil which is the isomer 3a which crystallizes by trituration with pentane, m.p. 90°C. In the same way, starting from 2b, the isomer 3b is obtained which is a white powder, m.p. 63°C. The 50:50 mixture of 3a+3b is an oil. The compounds of formula VIII indicated in the following table were obtained in the same way using the corresponding alcohols:

Example IV - Preparation of 1-[2-(2.4-dichlorophenyl)-4-ethylthiotetrahydrofuran-2-ylmethyl)-1H-1.2,4-triazole.

Compounds No. 7a and 7b

The bromide Ia (3.8 g) dissolved in dimethylsulfoxide (38 ml) containing water (2 ml) is treated with sodium hydrogen sulphide (2.8 g) for 2 hours. Powdered potassium hydroxide (3.3 g) is then added, followed by ethyl iodide (4 ml). After 10 min. stirring, the medium is diluted with water and extracted with ether. After drying and evaporation, the isomer 7a is obtained, which is a yellow oil (3.9 g) m.p. 88°C.

By working in the same way, starting from lb, 7b is obtained in the form of a pale yellow powder, m.p. 64°C. The mixture of isomers is an oil. The compounds of formula VIII listed in the following table were obtained in the same way, using the corresponding thiols:

Example V - Preparation of 1-f4-chloro-2-1 2 . 4-dichlorophenyl)-tetrahydrofuran-2-phenylmethyl)-1H-1,2,4-triazole.

Connections no, 13a and 13b

Step a)

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

The chlorohydrin obtained in step a) in example I dissolved in dichloromethane (150 ml) is treated with gaseous chlorine (13.4 g) at -15°C. The medium is then treated with a 37% strength sodium bisulphite solution (15 ml), washed with water, dried and then evaporated. A crude product is obtained in the form of a colorless oil (49.7 g) containing approximately 70% of the desired product in the form of a mixture of two diastereoisomers.

Step b)

Preparation of 1-(2,4-dichlorophenyl)-1-(2,3-dichloro-1-propane-yDoxirane).

A first method consists in dissolving the crude chlorohydrin

(10.3 g) obtained in step a) above in methanol (30 ml) and treat the solution with a solution of methanolic potassium hydroxide (12 ml) at a concentration of 2.55 x 10-<3> mol/ liter at room temperature . The precipitate is filtered off and the methanolic solution is evaporated under vacuum. The residue is purified using silica column chromatography. A colorless oil (7.4 g) is obtained.

Another method consists in dissolving the chlorohydrin (19.9 g) obtained in step a) of Example I in methanol (75 ml) and treating the solution with a potassium hydroxide (4.9 g) solution in methanol (20 ml) at normal temperature. After filtering off insoluble material and evaporation, the epoxide (17.1 g) is obtained in the form of a yellow oil. This epoxide is treated with chlorine until the yellow color (10.1 g) is permanent at -15°C. The medium is then washed with a sodium bisulphite top solution followed by water and then evaporated under vacuum. A yellow oil (20.8 g) consisting of a mixture of two diastereoisomers in the ratio 45:55 is obtained.

Step c)

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

The epoxide obtained in step b) (61.7 g) in 1-butanol (0.5 liter) is heated at 90°C for 6 hours in the presence of sodium triazolyl (18.6 g). The inorganic precipitate is filtered off and the butanol is evaporated. The residue is purified by silica column chromatography (48% ethyl acetate : 48% heptane : 4% methanol eluent) to give, in sequence, the first diastereoisomer 13a, m.p. 113°C, and then the other diastereoisomer 13b, m.p. 97°C. The 50:50 mixture of 13a+13b has a melting point of 90°C.

Example VI

Preparation of 1-(4-oxo-2-(2,4-dichlorophenyl)tetrahydrofuran-2-ylmethyl H-1H-1,2,4-triazole.

Connection 14

The alcohol 2a (37.7 g) is added at -60°C to a solution of dimethyl sulfoxide (17 ml) in dichloromethane (120 ml), treated at -60°C with a solution of trifluoroacetic anhydride (25.4 ml) in dichloromethane ( 60 ml). After the mixture has been kept at -60°C for half an hour, the temperature is allowed to rise to normal temperature and triethylamine (48 ml) is added. The medium is poured into water, extracted with dichloromethane and evaporated. A white powder (m.p. 91°C) is isolated with crystallization in ether.

A mixture of the ketone 14 (3.1 g), phosphorus pentachloride (2.3 g) and dichloromethane (30 ml) containing triethylbenzylammonium chloride (0.25 g) is stirred for 2 hours at room temperature until the starting material disappears. The medium is evaporated, the residue is diluted with water (100 ml), neutralized with sodium bicarbonate and extracted with ether. After drying and evaporation, the oily residue is recrystallized in isopropyl ether (twice). A white powder (0.6 g), m.p. 138°C. 1-(4,4-dichloro-2-(2,4-dichlorophenyl)tetrahydrofuran-2-ylmethyl)-1H-1,2,4-triazole, which is Compound No. 18.

Example VII - Preparation of 1-(4-methoxyamino-2-(2,4-dichlorophenyl)tetrahydrofuran-2-ylmethyl)-1H-1.2. 4-triazole.

Connection 15

The ketone of Example III (2 g) in ethanol (30 ml) is heated under reflux in the presence of methoxylamine hydrochloride (5.8 ml of a 25% solution in water) for 2 hours. The medium is diluted with water, extracted with dichloromethane and evaporated. The product is isolated by crystallization from a mixture of diisopropyl ether and heptane, in the form of a white powder, m.p. 108°C (mixture of the two geometric isomers).

Example VIII

The compounds in which

was produced in the same way.

Examples IX and the examples that follow illustrate the fungicidal uses of the compounds according to the invention.

In these examples, spraying of solutions or suspensions of active substances is carried out under conditions such that the spraying of a solution or suspension with a concentration equal to 1 g/litre corresponds to an average application of approximately 2 micrograms of active substance per cm<2> of leaf area of the plant.

Under the conditions of Example IX and the following examples, the illustrated compounds showed no phytotoxicity.

In these examples, a product is considered to provide complete protection against a fungal disease when the protection is at least 95%. Protection is considered good when it is at least 80% (but less than 95%), quite good when it is at least 70% (but less than 80%) and average when it is at least 50% (but less than 70%).

In the present context, the indicated percentage amounts, unless otherwise stated and with the exception of the percentage amounts relating to dividends, are on a weight percentage basis. In the case where the percentage amounts are expressed in relation to the stoichiometry, these are molar percentage amounts. With regard to concentrations, some of these are expressed as ppm (parts per million) which is equivalent to mg/liter.

Example IX - In vivo test on Botrvtis cinerea on tomato

An aqueous emulsion of the active substance to be tested, with the following composition, is prepared by fine grinding:

Active substance under test: 60 mg

"Step 80" (surfactant consisting of an oleate of a polycondensate of ethylene oxide with a sorbitan derivative) diluted to 10% strength in water 0.3 ml

as the volume is increased to 60 ml with water.

This aqueous emulsion is then diluted with water to achieve the desired concentration. 30 to 40-day-old greenhouse-grown tomato plants (variety Marmande) are treated by spraying with aqueous emulsions (called slurries) as defined above and at different concentrations of the compound being tested. The pre-test is repeated twice with each concentration.

After 24 or 48 hours, the leaves are cut and placed in two Petri dishes (diameter 14 cm) where the bottom was previously provided with a disc of moistened filter paper (5 leaves per dish).

The inoculum was then applied using a syringe by depositing drops (3 drops per leaf) of a spore suspension. This suspension of Botrytis cinerea spores was obtained from a 15-day-old culture which was then suspended in a nutrient solution (100,000 units/ml).

The determination was carried out 3 and 6 days after inoculation by comparison with an untreated control.

Under these conditions, at a dose of 1 g/liter, a good or total protection is observed with the compounds la, lb, la+lb, 3b, 5b, 6b, 8b, 9b, 12b, 13a, 13b, 13a+13b and 15 .

Example X - In vivo test with Erysiphe graminis on barley

(bvgg mold)

Barley, in pots, sown in ordinary soil, is treated in the step of 10 cm height by spraying with an aqueous emulsion (known as slurry) with the concentration indicated below. The experiment is repeated twice. After 24 hours, the barley plants are pollinated with Erysiphe graminis spores, as the spraying is carried out using diseased plants.

Readings are taken 8 to 14 days after inoculation.

Under these conditions, the following results are observed:

In a dose of 1 g/litre, good or total protection is achieved with la, lb, la+lb, 2a, 5b, 3a, 3b, 3a+3b, 4a, 4b, 5a, 5b, 6a, 6b, 7a+7b, 8a, 8b, 13a, 13b, 13a+13b, 14. 15, 17.

Example XI - In vivo test on "Puccinia recondita" responsible for wheat rust<pp>

Wheat, in pots, sown in ordinary soil, is treated in the step of 10 cm height by spraying with aqueous emulsions (referred to as slurries) of the same mixture as described in Example X and at different concentrations of the compound being tested. The experiment is repeated twice at each concentration.

After 24 hours, an aqueous suspension of spores is sprayed

(50,000 sp/ml) on the wheat. This suspension was obtained from

infected plants. The wheat was then placed for 48 hours in an incubation cell at approximately 18°C and 100% relative humidity.

After these 2 days, the relative humidity is lowered to 60%. The condition of the plants is determined between 11 and 15 days after inoculation, by comparison with the untreated control.

In a dose of 1 g/liter, good or total protection is achieved with compound la, lb, la+lb, 3a, 3b, 3a+3b, 5b, 6b, 7a, 7a+7b, 8b, 12b, 13a, 13b, 13a +13b, 15 and 17.

Example XII - In vivo test on "Piricularia orvzae" responsible for rlsvisnin<g>

Rice, in pots, sown in a 50:50 mixture of enriched peat and pozzolan, is treated in the step of 10 cm height by spraying with an aqueous emulsion (referred to as slurry) defined above at concentrations indicated below. The experiment is repeated twice. After 48 hours, treatment is carried out by applying a suspension of spores obtained in pure culture to the leaves.

Determination is carried out 8 days after inoculation. Under these conditions, the following results are observed: with a dose of 1 g/liter, good or total protection is obtained with compound la, lb, la+lb, 3a, 3b, 6a, 8a, 8b, 9a, 9b, 10b, lia, 11b , 12a, 12b, 13a, 13b, 13a+13b and 14.

Example XIII - In vitro test on seed fungi and soil fungi

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

1) Pyrenophorae avenae

2) Septoria nodorum

3) Helminthosporium teres

4) Fusarium roseum

5) Fusarium nivale

6) Fusarium culmorum

7) Rhizoctonia cerealis

8) Septoria tritici

9) Botrytis cinerea sensitive to carbenazim and cyclic imides 10) Botrytis cinerea resistant to carbendazim and cyclic imides

11) Pseudocercosporella herpotrichoides

12) Fusarium oxtysporud F. sp. melon ice cream

13) Rhizoctonia solani

14) Helminthosporium gramineum

The numbers listed before the names are used to represent these fungi in the following tables.

For each experiment, the procedure is as follows: a nutrient medium consisting of potato, glucose and agar (PDA medium) is introduced subcooled into a number of Petri dishes (30 ml per dish) after sterilization in an autoclave at 120°C.

During the filling of the bowls, an acetone solution of the active substance is injected into the subcooled medium to give the desired final concentration.

Petri dishes similar to the previous one, in which corresponding quantities of a nutrient medium that does not contain the active substance were filled, are taken as controls.

After 24 or 48 hours each dish is inoculated by depositing a fragment of mycelium that was written from a previous cultivation of the same fungus.

The dishes are stored for 2 to 10 days (depending on the fungus being tested) at 22°C and the growth of fungus in the dishes containing the active substance being tested is compared with the growth of the same fungus in the dishes used as a control.

For each compound tested, the degree of inhibition of the fungus in question, at a dose of 30 ppm, was determined in this way. The results are given in the following table.

Claims (4)

PATENT CLAIMS 1. Triazole compounds containing triazole groups, tetrahydrofuran and phenyl groups, characterized in that they have the general formula (I) in which Hal is a halogen atom, Y is a halogen atom and X^ stands for a halogen atom, hydroxy, lower alkoxy, lower alkylthio , phenoxycarbonyloxy, chlorolower alkylthio, oxo or methoxyimino. 2. Triazole compound as stated in claim 1, characterized in that Hal is Cl, Y is Cl and is Br. 3. Use of the triazole compounds specified in claim 1 or 2 as fungicides. 4. Means for controlling fungal diseases in crops, characterized in that it contains as active substance 0.5 - 95% by weight of a triazole compound as stated in claim 1 or 2 in addition to an inert carrier.