SI9300611A - Fungicidal 2-alcoxy-2-imidazolin-5-one derivatives - Google Patents

Abstract

2-Alkoxy-2-imidazolin-5-one derivatives of general formula (I): <IMAGE> in which: R<1> denotes an aryl radical, R<2> denotes an alkyl or haloalkyl radical, R<3> denotes an alkyl or haloalkyl group, R<4> denotes an aryl radical, R<5> denotes H or a formyl, acyl, aroyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulphonyl or arylsulphonyl radical. The invention also relates to the preparation of these compounds and to their use as broad-spectrum fungicides.

Description

RHONE-POULENC AGROCHIMIE

Fungicidal derivatives of 2-alkoxy-2-imidazolin-5-ones

The present invention relates to novel 2-alkoxy-2-imidazolin-5-one compounds for phytosanitary use. It also relates to processes for the preparation of these compounds and to products which, if appropriate, are useful as intermediates in the processes for their preparation. It further relates to the use of these compounds as fungicides, to fungicidal preparations based on these compounds, and to methods for combating fungal diseases in cultures using these compounds.

One object of the present invention is to propose compounds that exhibit improved properties in the treatment of fungal diseases.

Another object of the present invention is to propose compounds that exhibit a spectrum that is also improved in the field of fungal diseases.

We have now found that these purposes can be achieved in whole or in part by the products of the invention which are derivatives of 2-alkoxy-2-imidazolin-5-ones of the general formula (I):

in which

- R ¹ represents an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylene dioxyphenyl, each of these radicals being optionally substituted by 1 to 3 groups selected from the meanings for R ⁶ ;

- R ² represents an alkyl or haloalkyl radical having 1 to 3 carbon atoms,

- R ¹ and R ² may further form with the ring-attached carbon a carbocyclic or heterocycle having 5 to 7 atoms, these cycles may be fused with phenyl, each of these radicals in optionally substituted by 1 to 3 groups selected from the meanings for R ⁶ ;

- R ³ represents an alkyl or haloalkyl group having 1 to 3 carbon atoms;

- R ⁴ represents an aryl radical comprising phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylene dioxyphenyl, each of these radicals being optionally substituted by 1 to 3 groups selected from meanings for R ⁶ ;

- R ⁵ represents a hydrogen atom or a formyl or acyl radical of 2 to 6 carbon atoms, an aroyl or alkoxycarbonyl radical of 2 to 6 carbon atoms, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl;

- R ⁶ represents

- a halogen atom or

- alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio or alkylsulfonyl radical having from 1 to 6 carbon atoms, or

- cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkinyloxy, alkenylthio, alkynylthio radicals having 3 to 6 carbon atoms, or

- a nitro or cyano or thiocyanate group, or

- an amino radical optionally mono or substituted by an alkyl or acyl radical having from 1 to 6 carbon atoms or an alkoxycarbonyl radical having from 2 to 6 carbon atoms,

- phenyl, phenoxy, phenylthio, phenylsulfonyl or pyridyloxy radicals, optionally substituted by one or more of the following groups:

- a halogen atom or

- an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms, or

- cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkinyloxy, alkenylthio, alkynylthio having 3 to 6 carbon atoms, or

a nitro or cyano or thiocyanato group, or

- an amino radical optionally mono- or disubstituted by an alkyl or acyl radical having 1 to 6 carbon atoms or an alkoxycarbonyl radical having 2 to 6 carbon atoms,

- a phenyl, phenoxy, phenylthio, phenylsulfonyl or pyridyloxy radical, these radicals being optionally substituted by one or more of the following groups: -halogen halogen, or

- alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms ah

- cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkinyloxy, alkenylthio or alkynylthio radicals having 3 to 6 carbon atoms ah

a nitro or cyano or thiocyanato group, or

- an amino radical optionally mono- or disubstituted by an alkyl or acyl radical having 1 to 6 carbon atoms or an alkoxycarbonyl radical having 2 to 6 carbon atoms,

- phenyl, phenoxy, phenylthio, phenylsulfonyl or pyridyloxy radicals and their salt-converted forms.

The compounds of formula II below are preferred compounds

in which R ¹ to R ^{6 have the} same meanings as before.

Even more preferably, R ^{4 is} phenyl, substituted phenyl, pyridyl or substituted pyridyl, and R ⁵ represents a hydrogen atom or an acyl (e.g. acetyl) radical.

The compounds of formula I are obtained by reacting 2-alkylthio-2-imidazolin-5-ones of formula (III) with an alcohol R ³ OH in the presence of a strong base according to the scheme:

⁺ R ³ OH base

->.

solvent

Oh

O —R ³

NR ⁴

I

R ⁵ wherein R ¹ , R ² , R ³ and R ^{4 have the} same meaning as for Formula I and R ' ³ represents an alkyl group of 1 to 3 carbon atoms.

The alkali alcoholate R ³ O'M ⁺ , alkali hydroxide or a strong organic base may be used as the strong base. The metabolism is preferably carried out in alcohol R ³ OH as solvent using the corresponding sodium alcohol, this R ³ ONa ⁺ as base. The reaction is carried out at a temperature between 20 and 80 ° C. The 2-alkylthio-2-imidazolin-5-one of formula (III) is obtained according to the procedures described in European patent application EP 0 551 048. The acylation of compounds of formula I in which R ^{5 is} a hydrogen atom is carried out by conventional methods.

Salts of the compounds of formula I can be prepared by methods known per se.

The following examples are given to illustrate the compounds of the invention, the processes for their preparation and their antifungal properties.

The structures of all the products were determined by at least one of these spectral techniques: proton RMN spectrometry, carbon RMN spectrometry 13, infrared spectrometry and mass spectrometry.

In the table below, the methyl, ethyl, propyl, pyridyl, acetyl and phenyl radicals are represented by the symbols Me, Et, Pr, Py, Ac or. Ph, and soil. means melting point.

EXAMPLE 1: Preparation of Compound Nr. 2

In a 100 ml three-necked flask, metabolize 1.4 g (1.74 mmol) of sodium into 60 ml of ethanol under a dry nitrogen atmosphere. Then 4 g (1.28 mmol) of 4-methyl-2methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one are added. Reflux was heated for 6 h. The medium was cooled to ambient temperature and acidified with 0.4 ml of acetic acid. The medium was diluted with 300 ml of ethyl acetate. The organic solution was washed with water, then dried over magnesium sulfate and then concentrated under reduced pressure. We get red syrup. The product was purified by silica column chromatography. 1.25 g (31% yield) of compound no. 2 in the form of a slightly pink powder, melting at 106 ° C.

In the same manner, the following compounds were prepared:

Num. R6 R3 R4 R5 M.p. (° O 1 » Me Ph H 149 2 - Et Ph H 106 3 - nPr Ph H 80 4 4-C1 Me Ph H 140 5 - Me 2-Me-Ph H 118 6 4-C1 Me 2-Pyridyl H 150 8 - Me 2-Cl-Ph H 94 9 - Me 4-Cl-Ph H 124 11 3,4-di (MeO) Me Ph H 150 12 4-C1 Me 4-Cl-Ph H 176 13 4-C1 Me 4-F-Ph H 147 14 4-C1 Me 2-Cl-Ph H syrup 15 4-C1 Me 3-Cl-Ph H 147 16 4-C1 Me 4-Me-Ph H 162 17 4-C1 Me 3-Me-Ph H 116 18 4-Me Me Ph H 110 19 4-F Me Ph H 104

20 4-C1 Me 2-Me-Ph H syrup 21 4-F Me 3-Me-Ph H 114 23 4-F Me 2-Me-Ph H 88 24 4-Me Me 4-Cl-Ph H 166 25 4-Me Me 3-Cl-Ph H 155 27 4-Me Me 2-Cl-Ph H 86 28 4-Me Me 4-F-Ph H 124 29 4-F Me 3-Cl-Ph H 160 30 4-Me Me 4-Me-Ph H 155 31 4-F Me 4-Me-Ph H 149 32 4-Me Me 2-Me-Ph H 128 33 - Me 3-F-Ph H 121 34 4-Me Me 3-Me-Ph H 138 35 4-PhO Me 2-Me-Ph H 120 36 4-F Me 4-Cl-Ph H 142 37 - Me 4-F-Ph H 157 38 - Me 2,4-di (F) -Ph H 166 39 - Me 4-Me-Ph H 116 40 4-F Me 2-F-Ph H syrup 41 4-Me Me 2-F-Ph H 90 42 4-C1 Me 2-F-Ph H syrup

43 4-F Me 2-O-Ph H syrup 44 - Me 2,3-di (Me) -Ph H 140 45 - Me 3-0-2-pyridyl H 140 46 - Me 3-Me-Ph H 54 47 - Me 2-F-Ph H 136 48 - Me 3-Cl-Ph H 93 49 4-F Me 3-Me-2-pyridyl H 126 50 4-F Me 3-F-Ph H 120 51 The score is now 4-0 Me 3-F-Ph H 125 52 3-0 Me Ph H 155 53 3-0 Me 3-Me-Ph H 100 54 3-0 Me 3-Cl-Ph H 105 ⁵⁵ 3-0 Me 3-F-Ph H 135 56 3-0 Me 2-Me-Ph H 116 57 3-F Me Ph H 134 58 3-F Me 3-F-Ph H 115 59 - Me Ph Ac 121 60 3-F Me 3-Cl-Ph H 90 61 3-Me Me Ph H 98 62 3-Me Me 3-F-Ph H 118 63 4-PhO Me 2-Pyridyl H 146

64 2,4-diF Me Ph H 163 65 2,4-diF Me 3-F-Ph H 162 66 4-PhO Me Ph H 114 67 4-PhO Me 3-F-Ph H 56 68 2-C1 Me Ph H 214 69 - Me 4-PhO-Ph H 118 70 2-C1 Me 3-F-Ph H 201 71 2-F Me Ph H 172 72 2-F Me 3-F-Ph H 151 73 2,4-diF Me 3-Cl-Ph H 130 74 2-F Me 3-Cl-Ph H 151 75 4-iPr Me Ph H 132 76 4-PhO Me 3-Me-2-pyridyl H 142 77 4-iPr Me 3-F-Ph H 128 78 3-Me Me 3-Cl-Ph H 115 79 4-iPr Me 3-Cl-Ph H 139 80 4-Nr Me Ph H 138 81 4-NO2 Me Ph H 143 82 3-PhO Me Ph H syrup 83 2,4-di (F) -4-PhO Me 3-F-Ph H 71 84 2,4-di (F) -4-PhO Me Ph H 76

85 4-F-4-PhO Me Ph H 91

Compound no. 7:

Tal. = 73 ° C

Compound No.10:

Tal. = 86 ° C

Compound No.22:

Tal. = 71 ° C

Compound no. 86:

EXAMPLE 2 Plasmopara viticola (Vine Peronospora) In Vivo Test:

By fine grinding, prepare the aqueous suspension of the test substance with the following composition:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate polyoxyethylated sorbitan derivative) diluted to 10% in water: 0.3 ml

- Make up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of the active ingredient.

Seedlings i le (Vitis vinifera), Chardonnay varieties, are grown in pots. When the tare plants are 2 months old (stage 8 to 10 leaves, height 10 to 15 cm), they are sprayed with the above aqueous suspension.

The plants used as controls are treated with an aqueous solution containing no active ingredient.

After drying for 24 hours, each plant was infected by spraying an aqueous suspension of Plasmopara viticol spores obtained from a 4- to 5-day culture, which was then suspended with 100,000 units per cm ³ .

The infected plants are then incubated for 2 days at about 18 ° C in an atmosphere saturated with moisture, and then for 5 days at about 20 to 22 ° C at 90 to 100% relative humidity.

Evaluation is performed 7 days after infection compared with control plants.

Under these conditions, a good (at least 75%) or complete protection with temile compounds is observed at a dose of 1 g / l: 1, 3 to 21,23 to 25, 27 to 81, 83, 84 and 86.

EXAMPLE 3 In vivo test on Puccinia recondita (cereal rust):

By fine grinding, prepare the aqueous suspension of the test substance with the following composition:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate polyoxyethylated sorbitan derivative) diluted to 10% in water: 0.3 ml

- Make up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of the active ingredient.

The cereal in pots, sown on a 50/50 peat and ground soil substrate, is treated in a 10 cm height by spraying with the above aqueous suspension.

Spray the spores (100,000 spores / cm ³ ) over a grain of 24 hours. This suspension was obtained from infected plants. The cereals were then placed in an incubation cell at about 20 ° C and 100% -r »n relative humidity for 24 hours, and then for 7-14 days at 60% relative humidity.

Plant control is performed between days 8 and 15 after infection by comparison with the untreated control.

Under these conditions, good (at least 75%) or complete protection with temile compounds is observed at a dose of 1 g / l: 1,4 to 10,14,15,19 to 21, 23,25, 27 to 29, 31 to 33 , 36, 37, 39,40 to 48, 50 to 55, 57,58, 60,61, 63 to 67, 69,71 to 80, 82 to 84 and 86.

EXAMPLE 4: In vivo test for Phytophthora infestans (tomato mold):

By fine grinding, prepare the aqueous suspension of the test substance with the following composition:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate polyoxyethylated sorbitan derivative) diluted to 10% in water: 0.3 ml

- Make up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of the active ingredient.

Tomato plants (Marmande variety) are grown in pots. When the plants are 1 month old (stage 5 to 6 leaves, height 12 to 15 cm), they are treated by spraying the upper aqueous suspension with different concentrations of the test compound.

After 24 hours, infect each plant by spraying with an aqueous suspension of the spores (30,000 spores / cm ³ ) of Phytophthora infestans.

Following this infection, the tomato plants are incubated for 7 days at about 20 ° C in an atmosphere saturated with moisture.

days after infection, the results obtained in the case of plants treated with the test substance are compared with those obtained in the case of the plants used as controls. Under these conditions, a good (at least 75%) or complete protection with temile compounds is observed at a dose of 1 g / l: 1, 4 to 10, 15,18 to 21, 23, 28, 29, 31 to 33, 36, 37 , 39, 42 to 4 ^ 46 to 55, 57, 58, 60 to 67, 72 to 74,81,84 and 86.

EXAMPLE 5 In vivo test for Pyricularia oryzae (gray rice freckles):

By fine grinding, prepare the aqueous suspension of the test substance with the following composition:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate polyoxyethylated sorbitan derivative) diluted to 10% in water: 0.3 ml

- Make up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of the active ingredient.

The rice, sown in pots in a mixture of fortified peat and 50/50 pucola, is treated at a stage height of about 10 cm (corresponding to stage 2 to 3 leaves) by spraying with the above aqueous suspension.

After 24 hours, an aqueous suspension of Pyricularia oryzae spores obtained from a 15-day culture was applied to the leaves, which was then suspended with 100,000 units / cm ³ .

Rice plants were incubated for 24 hours (25 ° C, 100% relative humidity) and then in the observation cell under the same conditions for 5 days.

Assessment is performed 6 days after infection.

Under these conditions, good (at least 75%) or complete protection with these compounds is observed at a dose of 1 g / l: 1, 4 to 7,17,19, 20,23,25,29,31 to 33, 35 , 40 to 43,46, 47, 50, 52, 54,55, 57, 59, 61,63 to 67,71, 72, 74, 78,82,84 and 85.

EXAMPLE 6 Test in vivc on Septoria tritica (wheat leaf blight):

An aqueous suspension with a concentration of 1 g / l of the test substance is obtained by grinding 60 mg of the active ingredient in this mixture only:

- acetone: 5 ml

- surfactant (oleate of polycycethylated sorbitan derivative) diluted to 10%: 0 _; 3 ml, then adjust the volumer with water to 60 ml.

This aqueous suspension is then diluted with water to obtain the desired concentration of the active ingredient.

Cereal plants (Darius variety), sown on a peat and pozzolan 50/50 substrate and grown in a greenhouse at 10 to 12 ° C, are treated in stage 1 leaf (about 10 cm high) by spraying with the active substance suspension described above.

The plants used as controls were treated by spraying with an aqueous solution containing no active substance.

hours after treatment, the plants were infected by spraying with an aqueous spore suspension (500,000 spores / ml) obtained from 7 days old culture.

After infection, place the plants in a humid atmosphere at 18 ° C. Evaluation is performed 20 days after infection compared with control plants.

Under these conditions, good (at least 75%) or complete protection with compounds 1, 4 to 6, 9,19, 20, 23, 32, 33, 35 to 37, 40, 42 to 45 is observed at a dose of 1 g / l , 47, 48, 50, 52, 54, 55, 57,58,60,62 to 64,66,67,71 to 80,83,84 and 86.

These results clearly demonstrate the good fungicidal properties of the derivatives of the invention against plant fungal diseases caused by fungi belonging to a wide variety of families, such as Phycomycetes, Basidiomycetes, Ascomycetes, Adelomycetes or Fungi imperfecti, in particular vine feathers, tomatoes, and tomato rhizomes wheat leaf freckles as well as gray rice freckles.

For their practical use, the compounds of the invention are rarely used alone. Most often, these compounds are part of the preparations. These preparations, which are useful as fungicidal agents, contain as active ingredient a compound of the invention, as is already the case. described, in admixture with solid or liquid carriers acceptable in agriculture and / or surfactants which are also acceptable in agriculture. Particularly useful are inert and conventional carriers and conventional surfactants. These preparations are also part of the invention.

These preparations may also contain all kinds of other ingredients, such as e.g. protective skin; ide, adhesives, thickeners, thixotropic agents, penetration encounters, stabilizers, sequestration agents, etc. More generally, the compounds used in the invention can be combined with any solid or liquid additives that conform to conventional preparation techniques.

Unless otherwise stated, the percentages given in the present description are expressed as mass.

Generally, the compositions of the invention typically contain from 0.05 to about 95% by weight of the compound of the invention (hereinafter referred to as the active ingredient), one or more solid or liquid carriers, and optionally one or more surfactants.

The term carrier is used herein to describe an organic or mineral substance, natural or synthetic, with which a compound is combined to facilitate its use on a plant, on grains or on the ground. This carrier is therefore generally inert and must be acceptable in agriculture, in particular on the treated plant. The carrier may be solid (clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, especially butanol, etc.).

The surfactant may be an emulsion, dispersion or wetting agent of the ionic or non-ionic species or a mixture of such surfactants. For example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines, substituted phenols (especially alkylphenols, or aryl sulfenate derivatives) (especially alkyl esters), phosphoric acid esters of alcohols or polyoxyethylated phenols, fatty acid and polyol esters, derivatives of fore-compounds with sulfate, sulfonate and phosphate functions. The presence of at least one surfactant is generally essential if the compound and / or inert carrier is insoluble in water and if the carrier is water.

Thus, the preparations for agricultural use of the invention may contain the active ingredients of the invention within very wide limits, ranging from 0.05 to 95% by weight. Their surfactant content is preferably between 5 and 40% by weight. %.

These compositions according to the invention are inherently in very different, solid or liquid forms.

As forms of solid breasts. - Powders (containing up to 100% compound) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granular carrier, by powder granulation (in these latter cases, the content of the compound may be mentioned in these granules between 0.5 and 80%), effervescent compresses or tablets.

The compounds of formula (I) may also be used in powder form. A preparation containing 50 g of active ingredient and 950 g of talc may also be used. A preparation containing 20 g of active ingredient, 10 g of finely divided quartz and 970 g of talc may also be used. These ingredients are mixed and ground and the mixture is dusted.

Solution forms, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or spraying powders), pastes, may be mentioned as forms of liquid preparations or forms intended to form a liquid preparation when used. and gels.

Emulsifiable or soluble concentrates most commonly comprise 10 to 80% of the active ingredient, while containing emulsions or ready-to-use solutions, 0.001 to 20% of the active substance.

In addition to the solvent, the emulsifiable concentrates may, if necessary, contain 2 to 20% of suitable additives such as the stabilizers, surfactants, penetration agents, corrosion inhibitors, colorants or adhesives mentioned above.

These concentrates can be obtained by diluting with water emulsions at any desired concentration, which are particularly suitable for use on cultures.

For example, the composition of some emulsifiable concentrates is as follows:

Example CE1:

- active substance 400 g / l

- Alkali dodecylbenzene sulfonate 24 g / l

- oxyethylated nonylphenol with 10 ethylene oxide molecules 16 g / l

- cyclohexanone 200 g / l

- aromatic solvent q.s. for ί liter

According to the second formula of emulsifiable concentrate, we use:

Example CE 2:

- active ingredient 250 g

- epoxidized vegetable oil 25 g

- a mixture of alkylarylsulfonate and polyglycol ether and fatty alcohols 100 g

- dimethylformamide 50 g

- xylene 575 g

Concentrated suspensions, also useful by spraying, are prepared to give a stable, non-settling liquid product, typically containing 10 to 75% of the active ingredient, 0.5 to 15% of surfactants, 0.1 to 10% of thixotropic agents, 0 to 10% of suitable additives, such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrating agents and adhesives, and as a carrier water or an organic liquid in which the substance is slightly soluble or insoluble. Certain organic solids or mineral salts can be dissolved in the carrier to help prevent settling, or as freezing agents for water.

For example, the composition of a concentrated suspension.

Example SC 1:

- active ingredient 500 g

- polyethoxylated tristyrylphenol phosphate 50 g

- polyethoxylated alkylphenol 50 g

- Polycarboxyl sodium20 g

- ethylene glycol. 50 g

- Organopolysiloxane oil (antifoam) 1 g

- polysaccharide 1.5 g

-water 316.5 g

Moisturizing powders (or spraying powders) are usually prepared to contain from 20 to 95% of the active ingredient, and typically contain from 0 to 30% of a wetting agent in addition to the solid carrier and, if necessary, from 0.1 to 10% of one or more stabilizers and / or other additives such as penetrating agents, adhesives or anti-caking agents, dyes, etc. In order to obtain a spray powder or a wettable powder, thoroughly mix the ingredients in suitable mixers with additional substances and grind with mills or other suitable crushers. Spray powders with a wettability and suspendability are thus obtained. They can be suspended with water to any desired concentration and these suspensions are very advantageous especially for application to plant leaves. Pastes can be made instead of wettable powders. The conditions and methods for making and using these traps are similar to those for wettable or sprayable powders.

For example, here are various preparations of wettable powders (or spray powders):

Example PM 1:

- active substance 50% - ethoxylated fatty alcohol (wetting agent) 2.5% - ethoxylated phenylethylphenol (dispersant) 5% - chalk (inert carrier) 42,5%

Example PM 2:

- active ingredient 10%

- Synthetic branched-type oxo alcohol with 13C atoms, ethoxylated with 8 to 10 ethylene oxides (wetting) 0,75%

- neutral calcium lignosulfonate (dispersant) 12%

- calcium carbonate (inert filler) q.s. 100%

Example PM 3:

This wettable powder contains the same ingredients as in the previous example in the following proportions:

- active ingredient 75%

- o moistener 1.50%

- dispersant 8%

- calcium carbonate (inert filler) q.s. up to 100%

Example PM 4:

- active ingredient 90%

- ethoxylated fatty alcohol (wetting) 4%

- ethoxylated phenylethylphenol (dispersant) 6%

Example PM 5:

- active ingredient 50%

- Mixture of anionic and nonionic surfactants (wetting agent) 2.5%

- sodium lignosulfonate (dispersant) 5%

- kaolin clay (inert carrier) 42.5%

Aqueous dispersions and emulsions, for example, preparations obtained by diluting the wettable powder ah emulsifiable concentrate of the invention by means of water are included in the general scope of the present invention. Emulsions can be water-in-oil or oil-in-water types and may have a dense consistency, such as mayonnaise consistency.

The compounds of the invention can be formulated in the form of water-dispersible granules that are also present in the scope of the invention.

These dispersible granules with a apparent density, generally between about 0.3 and 0.6, have a particle size of generally between about 150 and 2000 and preferably between 300 and 1500 pm.

The active substance content of these granules is generally between about 1% and 90% and preferably between 25% and 90%.

The remainder of the granulate consists essentially of a solid filler and, optionally, of surfactants that give the granulate a water-dispersible property. These granules can be essentially of two different types depending on whether or not the remaining filler is soluble in water. If the filler is soluble in water, it may be mineral or preferably organic. Excellent results were achieved with urea. In the case of insoluble filler, it is a preferred mineral such as e.g. kaolin or bentonite. In this case, surfactants (in an amount of 2 to 20% by weight of granulate) are advantageously added, of which more than half form for example at least one dispersant, substantially anionic, such as alkali or alkaline earth polynaphthalene sulfonate or alkali or terrestrial alkali lignosulfonate and the remainder is formed by non-ionic or anionic wetting agents, such as alkali or terrestrial alkali alkyl naphthalene sulfonate.

Otherwise, although not necessary, other auxiliaries may be added, such as antifoams.

The granulate of the invention can be prepared by mixing the necessary ingredients and then granulating them according to various techniques known per se (irrigation, fluidized bed, atomizing, extrusion, etc.). Generally, we conclude with crushing followed by sieving to the particle dimension selected within the limits mentioned above.

It is preferably obtained by extrusion, doing the same as described in the examples below.

GDI example: Dispersible granulate

In the mixer mix 90 wt. % of the active substance and 10% of the urea in the beads. The mixture is then ground in a mill into plugs. A powder is obtained which is moistened with about 8 wt. % water.

The wet powder is extruded in an extruder with a perforated cylinder. A granulate is obtained which is dried, then crushed and sieved to retain only a granulate with dimensions between 150 and 2000 gm.

Example GD2: Dispersible granulate

In the mixer mix the following ingredients:

- active ingredient 75%

- wetting agent (sodium alkylnaphthalene sulfonate) 2%

- dispersant (sodium polynaphthalene sulfonate) 8%

- inert, water-insoluble filler (kaolin) 15%

This mixture was granulated in a fluidized bed in the presence of water, which would be dried, crushed and sieved to give granules with dimensions between 0.15 and 0.80 mm.

These granules can be used alone, dissolved or dispersed in water to obtain the required dose. They can also be used to prepare compounds with other ingredients, in particular fungicides, in the form of wettable powders or granules or aqueous suspensions.

As regards preparations adapted for storage and transport, they contain more than 0.5 to 95% by weight of the active substance.

The subject of the invention is also the use of the compounds of the invention for combating fungal diseases of plants by preventive or curative treatment of them or their habitat.

They are advantageously used in doses from 0.005 to 5 kg / ha and in particular from 0.01 to 1 kg / ha.

Claims (9)

PATENT APPLICATIONS 1. Compounds of 2-alkoxy-2-imidazolin-5-ones of the general formula (I) in which - R ¹ represents an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylene dioxyphenyl, each of these radicals being substituted by 1 to 3 groups selected from among the meanings for R ⁶ ; - R ² represents an alkyl or haloalkyl radical having 1 to 3 carbon atoms, - R ¹ and R ² may further form with the ring-attached carbon a carbocyclic or heterocycle having 5 to 7 atoms, these cycles may be fused with phenyl, each of these radicals in a given prime substituted with 1 to 3 groups selected from the meanings for R ⁶ ; - R ³ represents an alkyl or haloalkyl group having 1 to 3 carbon atoms; - R ⁴ represents an aryl radical comprising phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylene dioxyphenyl, each of these radicals being optionally substituted by 1 to 3 groups selected of meanings for R ⁶ ; - R ⁵ represents a hydrogen atom or a formyl or acyl radical of 2 to 6 carbon atoms, an aroyl or alkoxycarbonyl radical of 2 to 6 carbon atoms, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl; - R ⁶ represents - a halogen atom or - alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio or alkylsulfonyl radical having from 1 to 6 carbon atoms, or - cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkinyloxy, alkenylthio, alkynylthio radicals having 3 to 6 carbon atoms, or - a nitro or cyano or thiocyanate group, or - an amino radical optionally mono- or disubstituted by an alkyl or acyl radical having 1 to 6 carbon atoms or an alkoxycarbonyl radical having 2 to 6 carbon atoms, - phenyl, phenoxy, phenylthio, phenylsulfonyl or pyridyloxy radicals, optionally substituted by one or more of the following groups: - a halogen atom or - an alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms, or - cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkinyloxy, alkenylthio or alkynylthio radicals having 3 to 6 carbon atoms, or a nitro or cyano or thiocyanato group, or - an amino radical optionally mono or substituted by an alkyl or acyl radical having from 1 to 6 carbon atoms or an alkoxycarbonyl radical having from 2 to 6 carbon atoms, - phenyl, phenoxy, phenylthio, phenylsulfonyl or pyridyloxy radicals, and their salt-converted forms. Compounds according to claim 1, characterized in that they correspond to general formula II: NR ⁴ R ⁵ OR ³ in which R ¹ to R ^{6 have the} same meanings as in formula I. Process for the preparation of compounds according to claim 1, characterized in that the 2-alkylthio-2-imidazolin-5-one of formula (III) is reacted with an alcohol R ³ OH in the presence of a strong base according to the scheme: NR ⁴ I R ⁵ R ³ OH base R ² X OR ³ / solvent Λ 0 ^N NR ⁴ R ⁵ wherein R ¹ , R ² , R ³ and R ^{4 have the} same meaning as for formulas I and R ¹ represents an alkyl group of 1 to 3 carbon atoms. 4. Fungicidal compositions, characterized in that they, together with one or more solid or liquid carriers acceptable in agriculture, and / or surfactants which are also acceptable in agriculture, comprise one (or more) active ingredients which is (co) a compound of formula I according to claim 1. 5. Fungicidal compositions, characterized in that they contain, together with one or more solid or liquid carriers acceptable in agriculture, and / or surfactants also acceptable in agriculture, one (or more) active ingredients which is (co) a compound of formula II according to claim 2. Fungicidal compositions according to one of claims 4 or 5, characterized in that they contain from 0.5 to 95% by weight. % of the compounds according to any one of claims 1 or 2. 7. A method for treating cultures that are or may be attacked by fungal diseases, characterized in that an effective amount of a compound according to one of claims 1 to 2 or a preparation according to claims 4 to 6 is applied in a preventive or curative manner. A method of cultivation according to claim 7, characterized in that the effective dose is between 0.05 and 5 kg / ha. A method of treatment according to claim 8, characterized in that the effective dose is between 0.01 and 1 kg / ha. For RHONE-POULENC AGROCHIMIE: 23408-XI-93-MD PATENT OFFICE SUMMARY Fungicidal derivatives of 2-alkoxy-2-imidazolin-5-ones The invention relates to derivatives of 2-alkoxy-2-imidazolin-5-ones of the general formula (I): in which R ¹ represents an aryl radical, R ² represents an alkyl or haloalkyl radical, R ³ represents an alkyl or haloalkyl group, R ⁴ represents an aryl radical, R ⁵ represents H or a formyl, acyl, aroyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl or arylsulfonyl radical. The invention also relates to the preparation of these compounds and their use as broad-spectrum fungicides.