DK174326B1 - Triazole compounds, their use as fungicides and a means of controlling fungal diseases in crops - Google Patents

Description

and DK 174326 B1

The present invention relates to triazole compounds, and the particular feature of the compounds of the invention is that they have the general formula 5 n-.

\ __ I (,) ψ

Ha 1 wherein 15 Hal is a halogen atom Y is a halogen atom and X 1 represents a halogen atom, hydroxy, lower alkoxy, lower alkylthio, phenoxylcarboxyloxy, chloro lower alkylthio, oxo or methoxymino.

20

The invention also relates to the use of said compounds as fungicides, and the invention also relates to an agent ten. control of 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 claimed in claim 1 or 2 in addition to an inert support agent.

These and other features of the invention are set forth in the claims.

A variety of triazole compounds, especially fungicides, are already known and are described in European Patent Specification No. 151,084.

2 DK 174326 B1 O Rtl o ^ 5 _ Tn. ellerX / s' -v_

The present invention provides the present compounds with better properties for treating fungal diseases, in particular an improved field of application.

In the present disclosure with claims, the term lower for an organic group means that the group contains a maximum of 6 carbon atoms. The group may be straight or branched.

15

The compounds of formula I and the compounds which are optionally used as starting compounds in the process for their preparation, and which are defined in the description of the process, may exist in one or more isomeric forms depending on the number of asymmetric centers in the molecule. also all optical isomers, their racemic mixtures and their corresponding diastereoisomeric compounds. The separation of the diastereomers and / or optical isomers can be carried out in ways known per se.

The compounds of the invention can be used as preventative or curative agents against fungal species, especially of the type basidiomycetes, ascomycetes., Adelomycetes or fungi-imperfecti, especially rust, oidium, crack foot disease, fusariose, helminthosporiosis, septoriosis, rhizoctones in green vegetables. and especially the cereals such as oats, barley, wheat, rye and their hybrids and rice and maize. The present compositions are particularly active against fungi, especially of the type basidiomycetes, ascomycetes, adelomycetes or fungi imperfecti such as Botrytis cinerea, Erysiphe graminis, Puccinia recondita, Piricularia oryzae, Cercospore beticola, Puccinia striiformis,

Erysiphe cichoracearum, Fusarium oxysporum (melonis), Pyrenophora ave-nae, Septoria tritici, Ventirua inaequalis, Whetzelinia scierotiorum, Monilia laxa, Lycosphaerella fijiensis, Marssonina panettoniana, Alternaria solani, Aspergillus niger Penicillium expansum, Pestalozzia sp., Phialophora cinerescenes, Phoma betae, Phoma foveata, Phoma lingam, Ustilago may-dis, Verticillium dahliae, Ascochyta pisi, Guignardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia scicillinia, Sclerotinia .

10

They are also active against the following fungal species: Acrostalagmus koningi, Alternaria, Colletotrichum, Corticum rolfsii, Flygia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Hormodendron cladospo rioides, Lentinus degener or tigrinus, Lenzites quercina, Lenzites quercina, , Paecylomyces varioti., Pellicuiaria sasakii, Phellinus megalosporus, Polystictus sanguineus, Porla vaporarla, Sclerotium rolfsii, Stachybotris atra, Stereum, Stilbum sp. Trametes trabeam Trichoder-ma pseudokoningi, Trichothecium roseum.

20 The compositions in question are particularly interesting because of their wide-spectrum effects on diseases of the cereals (oidium, rust, crack foot disease, helminthosporiosis, septoriosis and fusariosis). They are also of great interest because of their effect on gray mold (Botrytis) and cer-cosporiosis, and for that reason they can be applied to as varied cultural plants 25 as vines, in commercial gardens and orchards, and to tropical cultural plants such as peanuts, coffee plants , banana palms, pican nuts and others.

In addition to the uses already mentioned above, the compounds of the invention exhibit, inter alia, an excellent biocidal effect against a whole host of other 30 microorganism species, among which may be mentioned but not limited to the fungi listed below: 4 DK 174326 B1

Puliularia as the species P. puilulans,

Chaetomium as the species C. globosum,

Aspergillus like the species Aspergillus niger,

Comophora as the species C. puteana.

5 Because of their biocidal effect, the compounds in question can effectively combat the microorganisms whose growth creates a range of problems in agriculture and industry. In this regard, they are particularly suitable for protecting vegetables and industrial products such as wood, leather, paints, paper, textiles, plastics and for use in recirculating water within the industry.

They are particularly suitable for protecting lignocellulosic products and especially wood in the case of furniture wood, timber or wood to be impregnated, such as fence posts, vines, railway sleepers and the like.

The present compositions used alone or as compositions defined above for the treatment of wood are usually prepared with organic solvents or may optionally be mixed with one or more known biocidal products, such as pentachlorophenol. metal salts, especially of copper, manganese, cobalt, chromium, zinc derivatives of inorganic acids or carboxylic acid (heptane, octane, naphthenic acid) organic complexes of tin, mercapto-benzotriazole, insecticides such as pyrethroids or chlorinated organic compounds.

25

They finally show excellent selectivity towards the cultures.

They are usually applied at doses of 0.005 to 5 kg / ha and especially 0.01 to 0.5 kg / ha.

In practice, the present compositions are rarely used alone. They are often part of compositions. The compositions which can be used for the protection of plants against fungal diseases or in regulatory compositions for plants, as active ingredient, contain a compound as described previously together with a fixed or liquid support acceptable in agriculture and / or surfactants which are also acceptable in agriculture. Particularly useful are inert and 5 common support materials and common surfactants.

The term "support materials" in the present specification with claims is understood to mean an organic or inorganic material, natural or synthetic, with which the active ingredient is brought together to facilitate its application to the plant, to the grain or to the soil. Thus, the support material is usually inert and The support material may be solid (clay soil, natural or synthetic silicates, silica, resins, coke, fertilizers, etc.) or liquids (water, alcohols, ketones, petroleum fractions, etc.). aromatic hydrocarbons or paraffins, chlorinated hydrocarbons, liquid gas, etc.).

The surfactant may be an emulsifier, dispersant, or ionic or nonionic plasticizer. Examples include salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolic sulfonic acids or naphthalenesulfonic acids, polyene condensates of ethylene oxide of fatty acids or fatty alcohols or fatty amines, substituted phenols (especially alkylphenols or arylphenols), ester acids, derivatives of aminoethylsulfonic acid (especially alkyl taurates), phosphorus esters of alcohols or polyoxyethylene phenols. The presence of at least one surfactant is usually necessary because the active ingredient and / or inert support material is not soluble in water and the applicator is water.

Thus, to be applied, the compounds of formula I are usually in the form of compositions; the compositions of the invention are themselves in different form, solid or liquid form.

6 DK 174326 B1

As solid Composition forms may be mentioned powders for powdering or dispersing (a content of the compound of formula I may be up to 100%) and granules, especially those obtained by extrusion, by striking, by impregnation on granulated support materials, by granulating out from a powder (the content of the compound of formula I may be in the granules between 1 and 80% in the latter cases).

As liquid compositions or intended to perform liquid compositions by their use, as solutions may be mentioned, in particular, concentrates soluble in water, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or powders for powdering), pastes,

The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or final solutions contain 0.01 to 20% of active material,

The compositions may also contain all kinds of other constituents, such as, for example, colloid protectors, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants, etc., as well as other active materials having pesticidal properties (especially insecticides or fungicides) or with properties favoring growth of plants (especially fertilizers) or plant regulators. Most often, the compounds of this invention can be found together with all kinds of solid or liquid additives 25, similar to the commonly used technique in the preparation of compositions.

For example, besides the solvent, the emulsifiable concentrates may also optionally contain 2 to 20% of additives suitable as stabilizers, as surfactants, as penetrants, as corrosion inhibitors, as dyes or as the adhesives mentioned above.

7 DK 174326 B1

The dose used in the case of the use as fungicides of the compounds of the present invention may vary widely, depending on the virulence of the fungi and the climatic conditions.

Generally, compositions containing 0.5 to 5,000 ppm active compound are suitable; the quantities are indicated for compositions prepared for use. ppm means "parts per million". The range 0.5 to 5,000 ppm corresponds to a value of 5 x 10'5 to 0.5% (wt%).

In the case of compositions intended for storage or transport, these more advantageously contain 0.5 to 95% (wt) active compound.

The compounds of the present invention may, for use in agriculture, contain the subject active material within very wide ranges ranging from 5.10 to 15% to 95% by weight.

Examples of the composition of some concentrates are given below:

Example F formulation) 1 20

Active ingredient 400 g / l

Alkaline dodecylbenzenesulfonate 24 g / l

Oxyethylnonylphenol for 10 molecules of ethylene oxide 16 g / l

Cyclohexanone 200 g / l 25 Aromatic solvent up to 1 liter

Another composition in the form of an emulsifiable concentrate is used for this: Example F 2

Active ingredient 250 g

Epoxidized vegetable oil 25 g 8 DK 174326 B1

Mixture of alcoylaryl sulfonate and polyglycol ether and one fatty alcohol 100 g

Dimethylformamide 50 g

Xylene 575 g 5

By starting from the concentrates, by dilution with water, emulsions can be obtained with all the desired concentrations which are particularly useful for application to the leaves.

Liquid compositions which can also be applied by spraying are prepared by obtaining a stable liquid product which does not trap, and it usually contains 10 to 75% of active material, 0.5 to 15% of surfactant, 0.1 to 10% thickener, from 0 to 10% of suitable additives, such as antifoam agents, corrosion inhibitors, stabilizers, penetrating and adhesive agents, and to support water or an organic liquid in which the active material is little or not soluble: certain organic solids materials and mineral salts may be dissolved in the support to help prevent sedimentation or as anti-gelling agents for the water 20 The wettable powders (or powders for powdering) are usually prepared in such a way that they contain 20 to 95% of active material and contain usually in addition to the solid support 0 to 5% wetting agent, 3 to 10% dispersant and optionally 0 to 10% of a wetting agent. or more stabilizers and / or other additives, such as penetrants, adhesives or antifouling agents, dyes, etc.

For example, various compositions for wettable powders are given below: Example F 3

Active material 50%

Calcium lignosulfonate (deflocculant) 5% 9 DK 174326 B1

Isopropyl naphthalene sulfonate (anionic wetting agent) 1%

Silica Antibody 5%

Kaolin (carrier) 39% 5

Another composition of powders with 70% uses the following ingredients:

Example F 4 10

Active material. 700 g

Natriumdibutylnaphthylsulfonat. 50 g

Condensation product 3/2/1 of naphthalenesulfonic acid, phenolic sulfonic acid and formaldehyde 30 g Kaolin 100 g

Chalk 120 g

Another 40% powder composition uses the following ingredients: 20

Active material 400 g

Sodium lignosulfonate 50 g

Sodium dibtuylene naphthalenesulfonate 10 g

Silica 540 g 25

Another composition of powder with 25% uses the following ingredients:

Example F 6 30

Active material 250 g

Calcium lignosulfonate 45 g

Equal weight mixture of chalk and hydroxyethyl cellulose 19 g

Natnumdibutylnapthalensulfonat. 15 g

Silica 195 g

Chalk 195 g 5 Kaolin 281 g

Another 25% powder composition uses the following ingredients.

Example F 7

Active material 250 g

Isooctylphenoxypolyoxyeihyleneethanol 25 g

Equal weight mixture of chalk and hydroxyethyl cellulose 17g

Sodium Aluminum Silicate 543 g

Silica 165 g

Another 10% powder composition uses the following ingredients:

Example F 8

Active material 100 g 25 Mixture of the sodium salts of sulphates of saturated fatty acids 30 g

Condensation product of naphthalenesulfonic acid and formaldehyde 50 g

Kaolin 820 g 30

To obtain the powders or wettable powders, the active materials are thoroughly mixed in a suitable mixer with the additional ingredients and comminuted with a mill or other suitable comminution apparatus. In this way, powders are obtained in which the wettability and suspension formation are advantageous; they can be converted into suspensions with water at any desired concentration, and the suspensions can be used advantageously especially when applied to the leaves of the plants.

5 Instead of wettable powders, pastes can be prepared. The preparation conditions and properties and use of these pastes are the same as for the wettable powders and for the powders.

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

15

Granules designed to be placed on the ground are usually prepared in such a way that they have a dimension between 0.1 and 2 mm and can be prepared by agglomeration or impregnation. Usually, the granules contain 0.5 to 25% of active material and 0 to 10% of additives, such as, for example, stabilizers, slow release agents, binders and solvents.

An example of the composition of a granule is the following, using the following ingredients: 25

Example F 9

Active material 50 g

Epichlorohydrin 2.5 g Cetyl ether and polyglycol 2.5 g

Polyethylene glycol 35 g

Kaolin (granulometry: 0.3 to 0.8 mm) 910 g 12 DK 174326 B1 In this case, the active compound is mixed with epichlorohydrin and dissolved with 60 g acetone; additional polyethylene glycol and cetyl ether and polygiycolen are added. The kaolin is wetted with the prepared solution and then the acetone is evaporated in vacuo. Such microgranules are advantageously used to control fungi in the soil.

The compounds of formula I may also be used as dust powders; one may also use a composition consisting of 50 g of active material and 950 10 g of talc; in addition, a composition consisting of 20 g of active material, 10 g of finely divided silica and 970 g of talc can be used; The ingredients are mixed and ground and the mixture is applied by powdering.

The following examples illustrate particular processes for preparing the compounds of the invention and the compounds. The nomenclature of the compounds is given according to French standard except that the numbering of the substituents is indicated in front of the substitutes themselves.

EXAMPLE I

Preparation of 1- [4-bromo-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole. Compound No. 1a. 1b and 1a + 1b Step a) Preparation of 1-chloro-2- (2,4-dichlorophenyl) -4-penten-2-ol:

An organic magnesium derivative is prepared by adding a solution of allyl bromide (110 ml) to ethyl ether (700 ml) and tetrahydrofuran (200 ml), to which 110 g of magnesium is added between 15 and 20 ° C over 3 hours. The mixture is heated to reflux for 30 minutes, decanted and washed with ether.

13 DK 174326 B1

To the organic phase is added a solution of α-trichloro-2,4-acetophenone (175 g) in tetrahydrofuran (250 g) at -30 ° C, neutralization with acetic acid. Wash with water, dry with sodium sulfate and concentrate by distillation in vacuo. A colorless oil (205 g) is obtained. Boiling point (3 x 10'2 5 mmHg) = 140 - 142 ° C.

Step 1 Preparation of 1- [2- (2,4-dichlorophenyl) -2-hydroxy-4-pentenyl] -1H-1,2,4-triazole A mixture of the product prepared above under step a) (106 g ), triazole (55 g) and potassium carbonate (160 g) are heated for 4 hours at 120 ° C in dimethylformamide (600 ml). The insoluble components are filtered off, washed with dimethylformamide and the reaction mixture is concentrated in vacuo. The residue, dissolved in methylene chloride, is washed with water and then concentrated. The compound is obtained by crystallization with ethyl acetate after dissolving in heptane. A solid pale pink material (97 g) is obtained, melting at 101 ° C.

Step c) Preparation of Compounds 1a and 1b The compound prepared in step b (35g) in chloroform (200ml) is treated at 0 ° C with bromine. After staining, the solvent is evaporated and the residue is redissolved in methanol. Then an aqueous solution of potassium carbonate is added until a basic pH is obtained. After evaporation in vacuo, 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 nearly equal amounts. Silicon column chromatography sequentially isolates the least polar isomer as # 1a: white crystals melting at 83 ° C, then the more polar isomer # 1b: white crystals melting at 94 ° C. After recrystallization, compound 1a melts at 96 ° C and compound 1b at 104 ° C. The mixture 50:50 of 1a and 1b melts at 74 ° C.

14 DK 174326 B1 In the same way, the following compounds are prepared, starting from the appropriate materials. 1- [4-bromo-2- (4-chlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole; 1c melts at 74 ° C, 1d melts at 78 ° C, and 1c + d melts at 69 ° C.

5

EXAMPLE II

Preparation of 1- [2- (2,4-Dichlorophenyl) -4-hydroxy-tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole Compounds Nos. 2a and Nos. 2b 10 g of isomer 1a of Example I, which is the least polar isomer, dissolved in 30 ml of chlorobenzene, is heated for 48 hours at reflux in the presence of 20 g of sodium benzoate in 30 ml of water and 1 g of phase transfer catalyst 'ADOGEN 464' methyl trialkylammomium chloride.

15

After dilution with ether, the organic phase is washed with water and evaporated in vacuo. The residue is then refluxed for 3 hours in methanol (100 ml) in the presence of 7 g of potassium. Cool, dilute with water, extract with ethyl acetate, wash to neutral reaction and purify the crude product obtained after concentration in vacuo by chromatography. The alcohol 2a is isolated in the form of a white powder (2.8 g) which melts at 193 ° C.

By working in the same way and by starting from the more polar isomer 1b prepared in Example 1, the optically active alcohol 2b is obtained, which appears 25 as a white powder melting at 162 ° C. The mixture 50/50 2a and 2b is an oil.

EXAMPLE III

Preparation of 1- (2- (2,4-dichlorophenyl) -4-ethoxytetrahydro-2-furanylmethylH-1H-1,2,4-triazole. Compounds Nos. 3a and 3b No. 174326 B1

The alcohol 2a (2.2 g) in solution in dimethyl sulfoxide (12 ml) is treated successively with 80 percent sodium hydride (0.42 g) and then with ethyl iodide (1.15 ml). After 15 minutes, the mixture is diluted with water and extracted with ethyl acetate. After washing with water, the solvent is evaporated, and the residue is purified by chromatography on silica to give a colorless oil, which is the isomeric 3a which crystallizes on trituration with pentane and melts at 90 ° C; similarly, starting from 2b, the isomer 3b, a white powder having a melting point of 63 ° C, is obtained. The 50:50 mixture of 3a + 3b is an oil. The compounds of formula VIII listed in the following table were prepared in the same manner using the appropriate alcohols.

No._Xi_X? Melting point ° C

4a H O-C- Φ (phenyl) 98 ° C

M

___ISLAND__

4b O-C-Φ (phenyl) H 140 ° C

II

__O___ 5a_H_Q-CH3_Oil_ 5b_0-CH3_H_Oil_ 6a _Jj_O-n-Pr_Oil_ 6b_O-n-Pr__H_Oil_ EXAMPLE IV 15

Preparation of 1- [2- (2,4-Dichlorophenyl) -4-ethylthio-tetrahydrofuran-2-ylmethyl] -1H-1,2,4-triazole, Compounds No. 7a 00, No. 7b

The bromide 1a (3.8 g) dissolved in dimethyl sulfoxide (38 ml) containing 2 ml of water is treated with sodium hydrogen sulfide (2.8 g) for 2 hours. Powdered potassium hydroxide (3.3 g) is then added followed by ethyl iodide (4 ml). After 10 minutes of stirring, the reaction mixture is diluted with water and extracted with ether. After drying and evaporation, the isomeric 7a, a yellow oil (3.9 g), m.p. 88 ° C is obtained.

By operating in the same way, but starting from 1b, 7b in the form of 5 is obtained a light yellow powder with a melting point of 64 ° C. The mixture of the isomers is an oil.

The compounds of formula (viii) in the following table were prepared in the same manner, starting from the appropriate thiols:

No, _Xi_X2_ Melting point 10

8a H S-CH3 96'C

8b S-CH3 H oil

9a H S-n-Pr 110 ° C

9b S-n-Pr H oil

10a H S-2-C1 It 127 ° C

10b S-2-C1Et H oil

11a H S-i-Bu 68 ° C

11b S-i-Bu H oil

12a H S-i-Pr 75 ° C

12b S-i-Pr H 65 ° C

EXAMPLE V

Preparation of 1- [4-Chloro-2- (2,4-dichlorophenyl) -tetra-hydrofuran-2-ylmethyl] -1H-1,2,4-triazole. Compounds No. 13a and No. 13b

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

The chlorohydrin obtained in step a) of Example I dissolved in dichloromethane (150 ml) is treated with gaseous chlorine (13.4 g) at -15 ° C. The reaction mixture is then treated with 37% sodium bisulfite solution (15 ml), washed with water, dried and then evaporated. The crude compound in the form of a colorless oil (49.7 g) containing about 70% of the desired compound in the form of a mixture of the two diastereoisomers is obtained in this way.

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

A first process consists of dissolving the crude chlorohydrin (10.3 g) obtained in step a) above in methanol (30 ml) and treating it with a solution of methanolic potassium hydroxide (12 ml) at a concentration of 22.5 x 10 3 10 mol / liter at room temperature. The precipitate is filtered off and the methanol solution is evaporated in vacuo. The residue is purified by silica column chromatography. A colorless oil (7.4 g) is obtained.

Another method consists of dissolving the chlorohydrin (19.9 g) obtained in step a) of Example I in methanol (75 ml) and treating it with a potassium hydroxide (4.9 g) solution in methanol (20 ml) at room temperature. . After filtration of the 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) persists at -15 ° C. Then the reaction mixture is washed with sodium bisulfite solution followed by water and evaporated in vacuo. A yellow oil (20.8 g) is obtained, consisting of a mixture of the two diastereoisomers at a ratio of 45:55.

Step C Preparation of 1- [4-Chloro-2- (2,4-dichlorophenyl) -tetrahydrofuran-2-ylmethyl] -1H-1,2,4-triazole

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

18 DK 174326 B1

EXAMPLE VI

Preparation of 1- [4-oxo-2- (2,4-dichlorophenyl) tetrahydrofuran-2-ylmethyl] -1H-1,2,4-triazole, Compound # 14

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 standing at -60 ° C for half an hour, let the temperature rise ten! room temperature, and triethylamine (48 ml) is added. The reaction mixture is poured into water and extracted with dichloromethane and evaporated. A white powder of melting point 91 ° C is obtained by crystallization with 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 at room temperature for 2 hours until the starting material has disappeared. The reaction mixture is evaporated, diluted with water (10 ml), neutralized with sodium bicarbonate and extracted with ether. After drying and evaporation, the oily residue is recrystallized from isopropyl ether (two times). 1- [4,4-Dichloro-2- (2,4-dichlorophenyl) -tetrahydrofuran-2-ylmethyl) -1H-1,2,4-triazole, Compound No. 18, is obtained as a white powder (0.6 g ) mp 138 ° C.

EXAMPLE Will 25

Preparation of 1- [4-methoxyimino-2- (2,4-dichlorophenyl) -tetrahydrofuran-2-ylmethyl] -1H-1,2,4-triazole. Compound # 15

The ketone of Example III (2 g) in ethanol (30 ml) is heated at reflux 30 in the presence of methoxylamine hydrochloride (5.8 ml to a 25% solution in water) for 2 hours. The reaction mixture is diluted with water extracted with dichloromethane and evaporated. The compound is isolated by crystallization 191 in a mixture of diisopropyl ether and heptane as a white powder, m.p. 108 ° C (a mixture of the two geometric isomers).

EXAMPLE VIII Similarly, the compounds are prepared wherein Xi = H (4-hydroxyimino), m.p. 195 ° C, (16), and

Xi = - <(4-isopropoxyimino) as an oil (17).

10

Example IX and the following show the fungicidal use of the subject compounds.

In these examples, the solutions or suspensions are injected with the active compounds under conditions such that the solution or suspension is equivalent to a concentration of 1 g / liter, equivalent to an average feed of about 2 µg of active compound per liter. cm leaf area of the plant.

Under the conditions used in Example IX and subsequent experiments, the compounds showed no phytotoxicity.

In these examples, a product is assumed to provide complete protection against fungal diseases if the protection is at least 95%; protection is assumed to be good if at least 80% (but less than 95%), and as relatively good if at least 70% (but less than 80%), and moderate if at least 50% (but less than 70%).

In the present, the percentages stated except where otherwise indicated, and 30 except those relating to the yields, are by weight percentages. In those cases where the percentages are expressed in relation to the stoichiometry, these are mole percentages. With regard to the concentrations, some are expressed in ppm (parts per million), which corresponds to mg / liter.

DK 174326 B1

EXAMPLE IX

fine in vivo test on Botrytis cinerea on tomato 5 A fine emulsion is prepared by fine grinding the active compound to be tested with the following composition:

The active compound to be tested: 60 mg of 10 Tween 80 (surfactant consisting of an oleate of a polycondensate to ethylene oxide with a sorbitan derivative) diluted to 10% strength in water: 0.3 ml, the volume then filled up to total 60 mi with water.

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

30 to 40 days old greenhouse-grown tomatoes (that of the species Marmande) are treated by spraying with aqueous emulsions (termed slurries) as defined above and at various concentrations that the compound to be investigated. The experiment is repeated twice with each concentration.

After 24 or 48 hours, the leaves are cut and placed in two Petri dishes (diameter 14 cm), the bottom of which is pre-equipped with a slice of moist filter paper (5 mixes per dish).

An inoculum is then applied by means of a syringe and droplets (3 drops per leaf) are deposited on a spore suspension. This suspension of Botrytis cinerea spores was obtained from a 15 day old culture, which was then slurried in a nutrient solution (100,000 units / ml).

Study is performed 3 and 6 days after inoculation by comparison with an untreated control.

21 DK 174326 B1

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

EXAMPLE X

In vivo trial and Ervsiphe araminis on bva (barley mildew)

Barley in plants grown in ordinary soil is treated at the stage where the plant is 10 10 cm high by spraying with an aqueous emulsion (termed slurry) at the concentration given below. The experiment is repeated twice. After 2.4 hours, the barley plant is sprayed with Erysiphe graminis spores, the dusting being carried out using sick plants.

15 Results are read 8 to 14 days after inoculation.

Under these conditions, the following results are observed.

At a dose of 1 g / liter, good or total protection was achieved with 1a, 1b, 1a + 20 1b, 2a, 2b, 3a, 3b, 3a + 3b, 4a, 4b, 5a, 5b, 6a, 6b, 7a + 7b, 8a, 8b, 13a, 13b, 13a + 13b, 14, 15, 17.

EXAMPLE XI

25 In vivo trial of "Puccinia recondita" responsible for wheat rust

Wheat in pots grown in plain soil is treated when the plant is 10 cm tall by spraying with aqueous emulsions (termed slurries) of the same compound and at different concentrations of the compounds to be tested. The experiment is repeated twice for each concentration.

After 24 hours, an aqueous suspension is sprayed onto spores (50,000 spores / ml) on the wheat plant; this suspension is obtained from infected plants. Here, the wheat is then placed in an incubator at approximately 18 ° C and 100% relative humidity for 48 hours.

After these 2 days, the relative humidity has dropped to 60%. The condition of the plant 5 is examined between the 11th and 15th day after inoculation by comparison with the untreated control. At a dose of 1 g / liter good or complete protection is obtained with the dry binders 1a, 1b, 1a + 1b, 3a, 3b, 3a + 3b, 5b, 6b, 7a, 7a + 7b, 8b, 12b, 13a, 10 13b, 13a + 13b, 15 and 17.

EXAMPLE XII

In vivo trial of "Piricularia orvzae". who is responsible for crack testimony 15

Rice in pots grown in a 50.50 mixture to enrich peat litter and puzzunan is treated when the plant is 10 cm high by spraying an aqueous emulsion (termed slurry) described above at the concentrations listed below. The experiment is repeated twice. After 48 hours, the treatment is carried out by applying a suspension to the leaves of spores obtained in pure culture.

Assessment that the experiment is performed 8 days after inoculation.

Under these conditions, the following results are seen: At a dose of 1 g / liter good or complete protection is obtained with compounds 1a, 1b, 1a + 1b, 3a, 3b, 6a, 8a, 8b, 9a, 9b, 10b , 11a, 11b, 12a, 12b, 13a, 13b, 13a + 13b and 14.

EXAMPLE XIII

30

In vitro experiments on seed fungi and soil fungi

The effect of the compounds of this invention was investigated on the following fungi responsible for diseases of cereal crops and other plants: 1) Pyrenophorae avenae 2) Septoria nodorum 3) Helminthosporium teres 5 4) Fusarium roseum 5) Fusarium level 6) Fusarium culmorum 7) Rhizoctonia cereal ice 8) Septoria tritici 10 9) Botrytis cinerea sensitive to carbendazim and cyclic imides 10) Botrytis cinerea resistant to carbendazim and cyclic imides 11) Pseudocercosporella herpotrichoides 12) Fusarium oxysporum F. sp. melonis 13) Rhizoctonia solam 15 14) Helminthosporium gramineum

The numbers in front of the names are the same ones used to indicate the fungi in the following tables.

For each experiment, the following method was used: a nutrient substrate consisting of potato, glucose and agar (PDA substrate) being subcooled in a series of Petri dishes (20 ml per dish) after sterilization in an autoclave at 120 ° C.

During the filling of the dishes, an acetone solution is injected into the active compound in the undercooled substrate to achieve the desired final concentration.

Petri dishes like the above, in which are poured similar amounts of nutrient substrate but which do not contain an active compound, are used as a control.

After 24 or 48 hours, each plate was seeded by applying a piece of mycelium derived from a pre-grown culture to the same fungus.

30 24 DK 174326 B1

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

5

For each compound tested, the degree of inhibition of the fungus is evaluated at a dose of 30 ppm. The following results are obtained in the table below.

Connection Sponge no.

1 2 3 4 5 6 7 1a 100 100 100 95 100 100 95 11b 100 90 100 100 100 100 90 1 a +1 b 100 95 100 95 100 100 90 2a 50 95 80 50 80 100 80 2b 80 110 80 50 90 90 80 3a 95 90 100 50 80 90 90 3b 95 95 100 80 90 100 90 3a + 3b 80 0 80 0 80 80 80 4a 90 0 90 80 80 90 90 4b 95 80 95 80 80 100 90 5a 50 90 50 50 50 50 50 5b 100 100 100 90 95 100 95 6a 50 90 50 50 50 50 50 6b 100 95 95 80 90 90 90 7a 95 95 95 0 0 0 50 7b 95 90 95 0 0 0 50 7a + 7b 50 95 50 0 0 0 50 8a 95 80 95 80 50 100 80 8b 100 90 95 80 80 90 80 9a 95 90 95 80 80 90 80 9b 80 95 95 0 0 80 80 25 DK 174326 B1 10a 80 0 80 50 90 95 80 10b 90 80 90 0 0 50 80 11a 90 50 95 0 0 0 80 11b 90 80 95 0 0 0 80 12a 90 80 95 0 80 80 80 12b 95 90 95 80 80 90 80 13a 95 95 100 95 100 100 90 13b 95 90 100 90 95 100 90 13a + 13b 100 95 100 150 100 100 95 J4_0_95 80 0 0 50 0 15 80 0 80 80 95 80 80 16 17 90 0 80 80 90 50 80 18 0 80 90 100 50 80 90

Compound Fungus No 1 2 3 4 5 6 7 1a 100 100 100 100 100 80 100 1b - 95 95 100 100 80 100 1a + 1b 100 95 95 100 100 90 95 2a 0 95 95 100 0 0 80 2b 0 80 50 100 80 0 80 3a 95 90 90 95 0 0 90 3b 100 95 100 95 80 80 95 3a + 3b 0 80 95 0 0 0 80 4a 0 95 95 0 0 0 90 4b 0 95 95 90 95 0 95 5a 0 0 0 100 0 0 50 5b 0 95 90 100 95 90 6a 0 50 50 100 0 0 50 26 DK 174326 B1 6b 50 95 95 100 80 80 95 7a 0 95 95 95 O 80 80 7b 0 90 95 90 O 50 50 7a + 7b - 95 95 100 50 80 50 8a O 80 80 80 80 80 95 8b O 95 95 90 80 80 95 9a O 90 90 90 80 90 95 9b O 95 90 100 80 80 50

10a 50 80 O O O O O

10b O 90 95 80 50 50, 90 11a OO 80 50 50 50 95 11b O 80 80 80 80 80 95 12a O 50 80 80 O 80 90 12b O 95 95 90 80 80 100 13a - 100 100 100 100 80 100 13b O 95 95 100 80 80 100 13a + 13b 50 95 95 100 100 80 95

14 - O O 95 O O O

15 O 80 80 O O O 80 16 17 O 00000 90 18 O 80 90 100 50 80 90

Claims (4)

1. Triazole compounds containing triazole groups, tetrahydrofuran and phenyl groups, characterized in that they have the general formula (I) 5 or Ha 1 wherein Hal is a halogen atom, Y is a halogen atom, and X 1 represents a halogen atom, hydroxy, lower alkoxy, lower alkylthio, phenoxylcarboxyloxy, chloro lower alkylthio, oxo or methoxymino. 20 Triazole compound according to claim 1, characterized in that Hal is Cl, Y is Cl. and Xt is Br. Use of the triazole compounds of claim 1 or 2 as fungicides. 25 4. A 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 claimed in claim 1 or 2 in addition to an inert support agent.