FR2706455A1 - Optically active fungicidal 2-imidazolin-5-one and 2-imidazoline-5-thione derivatives - Google Patents

Abstract

The present invention relates to new optically active 2-imidazolin-5-one and 2-imidazoline-5-thione derivatives, of general formula I in which: M represents O, S or optionally halogenated CH2 W represents O, S or the S=O group p = 0 or 1 R<1>, R<2> and R<4> represent a hydrocarbon, especially aryl, radical which is optionally substituted, in particular by halogen atoms R<3> is a hydrogen atom or an optionally halogenated C1-C2 alkyl radical R<5> is a hydrocarbon radical. The invention also relates to the preparation of these compounds and to their use as fungicides.

Description

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Optically active derivatives of 2-imidazoline-5-ones and 2-

imidazolin-5-thiones fungicides.

The present invention relates to novel optically active derivatives of 2-imidazoline-5-ones and 2-imidazoline-5-thiones for phytosanitary use, their preparation process and the compounds which may be used as intermediates in the preparation processes. It also relates to fungicidal compositions based on these compounds and a process for treating

fungal diseases of crops using these compounds.

Racemic compounds derived from 2-imidazoline-5-ones and 2-

imidazoline-5-thiones are described in European patent application No. 92 4204613 filed on December 16, 1992 and in French patent applications No. 92 08405 of July 2, 1992 and No. 92 14432 of November 25, 1992. These three

Patent applications have not yet been published to date.

It has now been discovered that one of the optical isomers of these compounds has a biological activity which is much greater than that of the other.

isomer and that of the racemic mixture.

An aim of the invention is therefore to provide novel useful compounds.

for the control of fungal diseases of crops.

Another object of the invention is to provide novel derivatives of 2-

imidazoline-5-ones and 2-imidazoline-5-thiones, active at a reduced dose by

compared to that of racemic derivatives.

It has now been found that these goals could be achieved through

products of the invention, which are optically active derivatives of 2imidazoline-

-ones or 2-imidazoline-5-thiones of general formula I: R2 * N (M) p -RS R 'N w N-R4 R5

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in which: W represents an oxygen or sulfur atom, or an S - O group; M represents an oxygen or sulfur atom, or a CH2 radical, optionally halogenated; p is an integer equal to 0 or 1; * means that asymmetric carbon ratome corresponding to a stereospecific configuration; R1 and R2 are different and represent: - an alkyl or haloalkyl radical of 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, mono alkylaminoalkyl, alkenyl or alkynyl radical of 2 to 6 carbon atoms or - a dialkylaminoalkyl radical or cycloalkyl of 3 to 7 carbon atoms or - an aryI radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl, optionally substituted with 1 to 3 groups chosen from R6 or - a arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above or - R1 and R2 can form, with the carbon to which they are linked on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused with a phenyl, optionally substituted with 1 to 3 groups chosen from R6; R3 represents a hydrogen atom or a C1-C2 alkyl radical, optionally halogenated; R4 represents:

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- the hydrogen atom, or - an alkyl group of 1 to 6 carbon atoms, or - an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group of 2 to 6 carbon atoms, or

- a dialkylaminoalkyl, alkoxycarbonylalkyl, or N- group

alkylcarbamoylalkyl of 3 to 6 carbon atoms, or - an N, Ndialkylcarbamoylalkyl group of 4 to 8 carbon atoms, or - an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzof , quinolinyl, isoquinolinyl, or methylene dioxyphenyl, optionally substituted by 1 to 3 groups chosen from R6, or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl having the definitions given above; R5 represents: - H, except when R4 is H, or - an alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl radical of 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioakyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl radical, alkoxyalkylsulfonyl, cyanoalkylsulfonyl of 2 to 6 carbon atoms or - an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl radical of 3 to 6 carbon atoms or - the formyl radical or - a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanocaryl, 3 to 6 carbon, alkenyl radical carbon atoms or - a cycloalkylcarbonyl radical of 4 to 8 carbon atoms or - a phenyl radical; arylalkylcarbonyl, in particular phenylacetyl and phenyl propionyl: arylcarbonyl, in particular benzoyl, optionally substituted with 1 to 3 groups from R6;

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thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or phenylthiolcarbonyl, the phenyl itself optionally being substituted by 1 to 3 groups from R6; alkylthiolcarbonyl; haloalkylthiolcarbonyl; alkoxyalkylthiolcarbonyl; cyanoalkylthiolcarbonyl; benzylthiolcarbonyl; furfurylthiolcarbonyl; tetrahydrofurfurylthiolcarbonyl; thienylmethylthiolcarbonyl; pyridylmethylthiolcarbonyl; or arylsulfonyl or - a carbamoyl radical optionally mono or disubstituted by: - an alkyl or haloalkyl group of 1 to 6 carbon atoms or - a cycloalkyl, alkenyl or alkynyl group of 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl group or cyanoalkyl of 2 to 6 carbon atoms or - a phenyl optionally substituted with 1 to 3 R6 groups; - a sulfamoyl group optionally mono or disubstituted by: - an alkyl or haloalkyl group of 1 to 6 carbon atoms or - a cycloalkyl, alkenyl or alkynyl group of 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl or cynoalkyl group of 2 with 6 carbon atoms or - a phenyl optionally substituted with 1 to 3 R6 groups; - an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or cycloalkylsulfonyl of 3 to 7 carbon atoms;

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- R4 and R5 taken together can also form, with the nitrogen atom to which they are attached, a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted by alkyl of 1 to 3 carbon atoms; -R6 represents: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical of 1 to 6 carbon atoms or - a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio radical of 3 to 6 carbon atoms or - the nitro or cyano group or - an amino radical optionally mono or disubstituted by an alkyl or acyl radical of 1 to 6 carbon atoms or alkoxycarbonyl of 2 to 6 carbon atoms - a phenyl or phenoxy radical or pyridyloxy, these radicals being

optionally substituted.

The invention also relates to salified forms acceptable in

agriculture of the compounds defined above.

According to a preferred variant of the invention, the optically active compounds according to the invention have the formula II: R2 N (M) p-R3 R6 w i-NNR Ir R's N R5 in which the different symbols have the same meaning as in formula I. i

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Finally, the compounds of the invention will be advantageously chosen from among

compounds of formula II for which W represents an oxygen atom.

The method of preparation of the compounds of formula I is indicated in the following paragraphs, according to two variant processes A and B. The symbols

represented in formula I, which appear in this description of the mode of

preparation, retain the same meaning as in the general definition of

invention, unless another definition is expressly attributed to them.

Variant A: First stage: In a first stage of this variant, the preparation of the optical isomers of formula I from amino acids which are optically pure or highly enriched in an enantiomer is described. The term “optically active compound highly enriched in a given enantiomer” is understood to mean a compound containing at least

%, preferably 95% of this enantiomer.

The optical isomers of formula I are prepared according to 3 series of

processes, depending on the meaning of group (M) p-R3.

1) Preparation of the compounds of formula I in which p = 1 and M - S and W = O-: The compounds of formula I in which p = 1 and M = S and W = O are prepared by reaction of the compound of formula III : HR 'y N R2. N-, wS

W N-R4

R5

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in which W represents an oxygen atom, with the compound of formula R3X, in which X represents the chlorine, bromine or diode atom or the sulfate group, or an alkylsulfonyloxy or arylsulfonyloxy group, alkyl and aryl being as defined more high for R1 and R2. The reaction is carried out in a solvent and in the presence of a base. As the base, an alcoholate can be used, for example potassium tert-butoxide, an alkali or alkaline earth hydroxide, an alkali carbonate or a tertiary amine. As solvent, it is possible to use ethers, cyclic ethers, alkyl esters, acetonitrile, alcohols with 1 to 3 carbon atoms, aromatic solvents, for example tetrahydrofuran with

temperature between -5 C and +80 C.

The compound of formula III, in which W represents an oxygen atom, can be prepared by a cyclization reaction, between an isothiocyanate of formula IV: R2 I,

RI-C-N = C = S

CO2R

in which R represents a C1-C4 alkyl, and a compound of formula V:

R4-N-NH2

R5 The cyclization reaction can be carried out in two ways: thermally: in this case the mixture of reactants is heated to a temperature between 110 C and 180 C in an aromatic solvent such as

toluene, xylene, chlorobenzenes.

- in a basic environment: one proceeds in the presence of an equivalent of a

base such as an alkali alcoholate, an alkali hydroxide or a tertiary amine.

Under these conditions, cyclization takes place at a temperature of between -10 and +80 C. As solvent, it is possible to use, in particular, ethers, ethers.

cyclics, alcohols, esters, DMF, DMSO.

The isothiocyanates of formula IV can be prepared according to one of the processes mentioned in Sulfur Reports Volume 8 (5) pages 327-375 (1989), from the α amino acid of formula VI:

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R2> NH2

R 'CO2H

in a manner well known to those skilled in the art.

2) Preparation of optical isomers of formula I in which p = 1 and M = 0 andW = O: The compounds of formula I in which p = 1 and M = 0 and W = O, are prepared by reacting the compound of formula I corresponding for which p = 1 and M = S, with the alcohol of formula R3OH, in a solvent, in the presence of a strong base, and at a temperature between 50 and 80 C. As strong base, it is possible to use an alkali alcoholate R30-Met. +, in which Met. + represents an alkali or alkaline earth metal, an alkali hydroxide or a strong organic base. The reaction is preferably carried out using alcohol as solvent.

R3OH and using the corresponding sodium alkoxide R30-Na + as the base.

3) Preparation of optical isomers of formula I in which p = 0: The compounds of formula I in which p = 0 and R3 is a hydrogen atom are obtained from the compound of formula VII:

R2 NH2

R 'H

NOT'

0 N-R4

R5 by reacting it with dimethylacetal of dimethylformamide (DMFDMA). The reaction is carried out at a temperature between 10 and

C, in excess DMFDMA.

The compound of formula VII is prepared from a compound of formula VIII:

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R2 NH3 + C1-

Rj> 3 Cl o by reaction of the latter with the compound of formula V, at a temperature between -20 and 40 C, in a solvent consisting of a cyclic or non-cyclic ether, optionally in the presence of a base. The base is chosen from nitrogenous organic bases such as triethylamine or pyridine. The compounds of formula VIII can be obtained from cO amino acid of formula VI by considering the method described by S. Levine

in J. Am. Chem. Soc. of 1953, volume 76, page 1392.

The optically active compounds of formula I in which R3 is a C1-C2 alkyl radical, optionally halogenated, and in which p = 0 or p = i and M = CH2 are obtained from the compound of formula IX:

R2 N, R3

R 'I

/ 0 o in which R3 represents a C1-C3 alkyl radical, by reaction of the latter with the compound of formula V, under conditions deduced, by analogy, from the method described in the article by J. P.

Branquet et al. in Bull. Soc. Chim. de France, 1965, (10), pp 29422954.

This same article gives a procedure at the end of which the compound

of formula IX can be prepared from the α amino acid of formula VI.

Second step: In this second step, the mode of access to the (x optically pure or highly enriched amino acids of formula VI used in the previous step is specified. These ca amino acids can be obtained according to one of the following methods:

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- Or by resolution of the corresponding racemates, by recrystallizing diastereoisomers, as described by MacKenzie and Clough in J. Chem. Soc. 1912 pages 390-397; - or by diastereoselective synthesis then removal of the chiral copula, as described by M. Chaari, A. Jenhi, J. P. Lavergne and P. Viallefont in

Tetrahedron 1991 Volume 4 pages 4619-4630.

- or by enzymatic resolution of the racemic amide, a method for which the following references may usefully be consulted: R. M. Kellog, E. M. Meijer et al. J. Org. Chem. 1988 Volume 53, pages 1826-1828 D. Rossi and A. Calcagni Experimentia 1985 volume

41 pages 35-37.

Variant B: According to a second variant of the process for preparing the optical isomers of formula I, they are obtained from the corresponding racemic compounds, by high performance liquid chromatography on a chiral stationary phase. A PIRKLE-type chiral stationary phase with a D-graft

phenyl glycine is preferred.

The racemic compounds corresponding to formula I are prepared according to the methods described in the three patent applications cited in the part

introductory part of this text.

A subject of the invention is also new compounds which are useful in particular as intermediates in the preparation of the compounds of formula L These intermediates have the formulas III, IV, VI, VII, VII: H

R2 NC S

R 'R2

I.

A.R I 1 /.

R'-C-N-C-S

W N-R4 I

C02R

R3

I

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R2 NH2

R2 \ NH2 R N

o N-R4

R 'CO2H

VI Vii R

R2 NH + C-

R 'Cl o VIII in which R1 to R5 have the same meanings as in general formula I of the invention, and the compound of formula IX:

R2 * N R3

R'4 / 0 or lx i0 iX in which Ri and R2 have the same meaning as above and

R3 represents an optionally halogenated C1-C3 alkyl radical.

The examples below illustrate the optically active derivatives of formula

I and their method of preparation.

The structures of all the illustrated derivatives were established using at least one of the following spectral techniques: proton NMR spectrometry, carbon 13 NMR spectrometry, infrared spectrometry and

mass, as well as the usual methods of measuring rotational powers.

Example 1: Preparation of the (+) and (-) enantiomers of the compound of formula:

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Me Ny SMe QN.N N-Ph H The corresponding racemic compound is prepared according to a procedure similar to that described in Example 1 of patent application No. 92 4204613 of December 16, 1992, already cited. This racemic compound is dissolved in an eluent mixture composed of n heptane, isopropanol and dichloromethane,

in the respective weight proportion of 93, 5, and 2%.

2.3 ml of the mixture thus obtained are injected into the high performance chiral chromatographic column, having the following characteristics: column of PIRKLE type, with a diameter of 10 mm and a length of 250 mm; support: 5 μm 100 angstrom silica with ionic phenyl glycine D grafting. The chosen flow rate is 10 ml / min and the detector used is a UV detector

at 250 nm.

The enantiomerically pure compounds are recovered by

fractionation and concentration of pure fractions.

The physical characteristics of the enantiomers obtained, namely the melting point PF, the optical rotation [a] D20 measured in degrees for the compound dissolved in ethanol at a concentration of 0, have been collected in the table below, 5 g per 100 ml, and the retention time tR: Compound n PF (C) [o] p20 tR (in minutes) 1 138 + 60.7 + or - 1.3 5.73 2 138 -59.6+ or - 0.9 6.55 Example 2: Preparation of the (+) and (-) enantiomers of the compound of formula:

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Me N yOMe QN.N N-Ph I H The corresponding racemic compound is prepared according to a procedure similar to that described in Example I of patent application No. 92 14432 of November 25, 1992, already cited. The corresponding (+) and (-) enantiomers (respectively compounds n 3 and 4) are obtained by proceeding in the same manner as above. The volume injected into the chiral column is 1.5 ml. The optical rotation is measured after dissolving the compounds in methanol and is shown with the other physical characteristics, identical to those determined previously in the table below: Compound n PF (C) [CO]) 20 tR (in minutes) 3 132 + 51.3 + or - 1.2 9.89 4 132 - 53.2 + or - 1.3 11.17 The following examples illustrate the fungicidal properties of the compounds according to the invention nl to 4. In these examples, the racemic mixture corresponding to the enantiomeric compounds 1 and 2 is noted 1 + 2. Likewise the racemic mixture

corresponding to compounds 3 and 4 is noted 3 + 4.

Example B 1: In vivo test on Puccinia recondita (wheat rust): An aqueous suspension of the active material to be tested is prepared, by fine grinding, having the following composition: - active material: 60 mg - surfactant Tween 80, ( oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml

- make up to 60 ml of water.

The active material to be tested is either one of the 2 enantiomers according to

the invention, or the corresponding racemic mixture.

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This aqueous suspension is then diluted with water to obtain the

desired concentration of active ingredient.

Wheat of the Talent variety, in pots, sown on a 50/50 pozzolan peat soil substrate, is treated at the 10 cm height stage by spraying the above aqueous suspension. After 24 hours, an aqueous spore suspension (100,000 sp / cm3) is sprayed onto the wheat; this suspension was obtained from contaminated plants. The wheat is then placed for 24 hours in an incubation cell at about 20 C and 100% relative humidity, then for 7 to 14 days at 60%

relative humidity.

The condition of the plants is checked between the 8th and 15th day after contamination, by comparison with an untreated control. The concentration of active material tested, CI75, for which one observes

75% inhibition of the disease.

Under these conditions, an IC75 of: 330 ppm is measured for the racemic compounds 1 + 2 and 3 + 4,

greater than 1000 ppm for enantiomeric compounds (-

) n 2 and n 4, At 37 ppm and 110 ppm respectively for the compounds

enantiomers (+) n 1 and n 2.

Example B2: In vivo test on Phytophthora infestans (tomato mildew): An aqueous suspension of the active material to be tested is prepared, by fine grinding, having the following composition: - active material: 60 mg surfactant Tween 80, (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml

- make up to 60 ml of water.

The active material to be tested is chosen from the same compounds as in

the previous example.

This aqueous suspension is then diluted with water to obtain the

desired concentration of active ingredient.

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Tomato plants (Marmande variety) are grown in pots.

When these plants are one month old (5 to 6 leaf stage, height 12 to 15 cm), they are treated by spraying the above aqueous suspension and at various

concentrations of the test compound.

After 24 hours, each plant is contaminated by spraying with an aqueous spore suspension (30,000 sp / cm3) of Phytophthora infestans. After this contamination, the tomato plants are incubated

for 7 days at 20 C in an atmosphere saturated with humidity.

Seven days after contamination, the results obtained in the case of plants treated with the active material to be tested are compared with those obtained in the case of plants used as controls. The concentration of matter is then determined

active tested, CI75, for which a 75% inhibition of the disease is observed.

Under these conditions, an IC75 is measured of: 15.110 ppm for the racemic compound 1 + 2, 330 ppm for the racemic compound 3 + 4,

greater than 1000 ppm for enantiomeric compounds (-

) n 2 and n 4, respectively 37 ppm and 110 ppm for the compounds

(+) n l and n 3 enantiomers.

The invention also relates to compositions for the protection of.

plants against fungal diseases, comprising, in combination with one or more

solid or liquid supports acceptable in agriculture and / or surfactants

active ingredients also acceptable in agriculture, one (or more) active material which is a compound of formula I. In fact, for their practical use, the compounds according to the invention are

rarely used alone. Most often these compounds form part of compositions.

These compositions, which can be used as fungicidal agents, contain as active material a compound according to the invention as described above in a mixture with the solid or liquid supports, acceptable in agriculture and the surfactants also acceptable in agriculture. In particular, the inert and customary supports and the customary surfactants can be used. These

compositions also form part of the invention.

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These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestering agents, etc. More generally, the compounds. used in the invention can be combined with all the solid or liquid additives corresponding to the

usual techniques of formulation.

In general, the compositions according to the invention usually contain from 0.05 to 95% approximately (by weight) of a compound according to the invention (hereinafter called active material), one or more solid supports or

liquids and, optionally, one or more surfactants.

By the term “support”, in the present description, is meant an organic or inorganic material, natural or synthetic, with which the compound is combined to facilitate its application to the plant, to seeds or to the ground. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or

liquid (water, alcohols, especially butanol etc ...).

The surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines. , substituted phenols (in particular alkylphenols or arylphenols), salts of esters of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of alcohols or of polyoxyethylated phenols, esters of acids fatty acids and polyols, the sulphate, sulphonate and phosphate-functional derivatives of the above compounds. The presence of at least one surfactant is generally essential when the compound and / or the inert support is not

soluble in water and that the carrier for the application is water.

Thus, the compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 0.05% to 95% (by weight). Their surfactant content is

advantageously between 5% and 40% by weight.

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These compositions according to the invention are themselves under

quite diverse forms, solid or liquid.

As forms of solid compositions, mention may be made of powders for dusting (with a compound content of up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation with from a powder (the compound content in these granules being between 0.5 and 80% for the latter cases), the tablets or

effervescent tablets.

The compounds of formula (I) can also be used in the form of powders for dusting; it is also possible to use a composition comprising 50 g of active material and 950 g of talc; it is also possible to use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by powdering. As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, powders. wettable (or

spray powder), pastes, gels.

Emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, emulsions or ready-to-use solutions.

the application containing, for its part, 0.001 to 20% of active material.

In addition to the solvent, emulsifiable concentrates may contain, when necessary, 2 to 20% of suitable additives such as stabilizers, surfactants, penetrators, corrosion inhibitors,

dyes or adhesives previously mentioned.

From these concentrates, emulsions of any desired concentration, which are suitable, can be obtained by dilution with water.

especially when applying to crops.

As an example, here is the composition of some emulsifiable concentrates:

Example CE 1:

- active ingredient 400 g / l

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- alkaline dodecylbenzene sulfonate 24 g / l - oxyethylated nonylphenol containing 10 molecules of ethylene oxide 16 g / l - cyclohexanone 200 g / l - aromatic solvent q.s.p. 1 liter According to another emulsifiable concentrate formula, we use:

Example CE 2 - active ingredient 250 g - epoxidized vegetable oil 25 g - mixture of

alkylaryl sulfonate and polyglycol ether and fatty alcohols 100 g dimethylformamide 50 g - xylene 575 g The concentrated suspensions, also applicable as a spray, are prepared in such a way as to obtain a stable fluid product which does not settle and they contain usually 10 to 75% active material, 0.5 to 15% surfactants, 0.1 to 10% thixotropic agents, 0 to 10% suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is little or not soluble: some organic solids or inorganic salts can be dissolved in the holder to help prevent sedimentation or as an antifreeze for

the water.

By way of example, here is a concentrated suspension composition: Example SC 1: - active material 500 g polyethoxylated tristyrylphenol phosphate 50 g - polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g

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- organopolysiloxane oil (defoamer) 1 g - polysaccharide 1.5 g - water 316.5 g Wettable powders (or spray powder) are usually prepared so that they contain 20 to 95% active ingredient, and they usually contain , in addition to the solid carrier, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersing agent, and, when necessary, from 0.1 to 10% of one or more stabilizers and / or other additives, such as

penetrating agents, adhesives, or anti-caking agents, coloring agents, etc ...

To obtain spray powders or wettable powders, the active ingredients are intimately mixed in the appropriate mixers with the additional substances and are ground with mills or other suitable grinders. In this way, spraying powders are obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and these suspensions are very useful.

advantageously in particular for application to the leaves of plants.

Instead of wettable powders, you can make pastes. The conditions and methods of making and using these pastes are similar

to those of wettable powders or powders to spray.

By way of example, here are various compositions of wettable powders (or spray powders):

Example PM 1

- active material 50% - ethoxylated fatty alcohol (wetting agent) 2.5% ethoxylated phenylethylphenol (dispersing agent) 5% - chalk (inert support) 42.5% Example PM 2: - active material 10% - synthetic oxo alcohol of the type branched, C13 ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75% - neutral calcium lignosulphonate (agent

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dispersant) 12% - calcium carbonate (inert filler) q.s.p. 100%

Example PM 3:

This wettable powder contains the same ingredients as in the previous example, in the following proportions: - active material 75% - wetting agent 1.50% - dispersing agent 8% - calcium carbonate (inert filler) q.s.p. 100%

Example PM 4:

- active ingredient 90% - ethoxylated fatty alcohol (wetting agent) 4% ethoxylated phenylethylphenol (dispersing agent) 6%

Example PM 5:

- active material 50% - mixture of anionic and nonionic surfactants (wetting agent) 2.5% - sodium lignosulphonate (dispersing agent) 5% - kaolin clay (inert support) 42.5% * Aqueous dispersions and emulsions , for example the compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope 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 such as that of a "tmayonnaise". The compounds according to the invention can be formulated in the form of water dispersible granules also included within the scope of the invention. These dispersible granules, with a bulk density generally between about 0.3 and 0.6, have a particle size generally

between approximately 150 and 2000 and preferably between 300 and 1500 microns.

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The active ingredient content of these granules is generally

between approximately 1% and 90%, and preferably between 25% and 90%.

The remainder of the granule is essentially composed of a solid filler and optionally of surface-active adjuvants which give the granule properties of dispersibility in water. These granules can be essentially

of two distinct types depending on whether the charge retained is soluble or not in water.

When the filler is water-soluble, it can be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, the latter is preferably mineral, such as, for example, kaolin or bentonite. It is then advantageously accompanied by surfactants (in an amount of 2 to 20% by weight of the granule), more than half of which is, for example, constituted by at least one dispersing agent, essentially anionic, such as a polynaphthalene. alkali or alkaline earth sulphonate or an alkali or alkaline earth lignosulphonate, the remainder consisting of nonionic wetting agents or

anionic such as an alkali or alkaline earth alkyl naphthalene sulfonate.

Moreover, although this is not essential, we can add

other adjuvants such as defoamers.

The granule according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). This generally ends with crushing followed by sieving to the particle size chosen within the limits mentioned above. It is also possible to use granules obtained as

previously then impregnated with a composition containing the active material.

Preferably, it is obtained by extrusion, operating as indicated.

in the examples below.

Example GD1 Dispersible granules In a mixer, 90% by weight of active material is mixed and

*% urea in beads. The mixture is then ground in a pin mill.

A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roll extruder. A granule is obtained which is dried, then crushed and sieved, so as to keep respectively only the granules with a size between 150 and 2000 microns.

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Example GD2: Dispersible granules In a mixer, the following constituents are mixed: - active ingredient 75% - wetting agent (sodium alkylnaphthalenesulphonate) 2% - dispersing agent (sodium polynaphthalenesulphonate) 8% - inert filler insoluble in water (kaolin) 15% This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between

0.15 and 0.80 mm.

These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active ingredients, in particular fungicides, the latter being in the form of wettable powders, or of

granules or aqueous suspensions.

As regards the compositions suitable for storage and transport, they more preferably contain from 0.5 to 95% (by weight) of

active substance.

A subject of the invention is also a process for the treatment of cultures affected or liable to be affected by fungal diseases, characterized in that one applies, in a preventive or curative manner, an effective amount of an optically active compound of formula I. The compounds of formula I are advantageously applied in dosages

from 0.005 to 5 kg / ha, and more specifically from 0.01 to 1 kg / ha.

23 2706455

Claims (15)

1. Optically active derivatives of 2-imidazoline-5-ones or 2- imidazoline-5-thiones of general formula I: R2-, N (M) -R3 R 'v N W N-R4 l R5 in which: W represents an oxygen or sulfur atom, or an S = O group; M represents an oxygen or sulfur atom, or a CH2 radical, optionally halogenated; p is an integer equal to 0 or 1; * means that the corresponding asymmetric carbon atom has a stereospecific configuration; R1 and R2 are different and represent: - an alkyl or haloalkyl radical of 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, mono alkylamninoalkyl, alkenyl or alkynyl radical of 2 to 6 carbon atoms or - a dialkylaminoalkyl radical or cycloalkyl of 3 to 7 carbon atoms or 24 2706455 - an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl, optionally substituted by 1 to 3 groups chosen from R6 or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfuryl radical, the terms aryl and alkyl having the definitions given above or - R1 and R2 can form, with the carbon to which they are linked on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, these rings possibly being fused with a phenyl, optionally substituted with 1 to 3 groups chosen from R6; R3 represents a hydrogen atom or a C1-C2 alkyl radical, optionally halogenated; R4 represents: - the hydrogen atom, or - an alkyl group of 1 to 6 carbon atoms, or - an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group of 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonylalkyl, or N- group alkylcarbamoylalkyl of 3 to 6 carbon atoms, or - an N, Ndialkylcarbamoylalkyl group of 4 to 8 carbon atoms, or - an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzof , quinolinyl, isoquinolinyl, or methylene dioxyphenyl, optionally substituted by 1 to 3 groups chosen from R6, or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsuifonylalkyl radical, the terms aryl and alkyl having the definitions given above; -R5 represents: 2706455 - H. except when R4 is H, or - an alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl radical of 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioakyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxy, cyulfanoalkylsulfonylsulfon radical from 2 to 6 carbon atoms or - an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl radical of 3 to 6 carbon atoms or - the formyl radical or - a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl, alkynylcarbonyl radical of 3 to 6 carbon atoms or - a cycloalkylcarbonyl radical of 4 to 8 carbon atoms or - a phenyl radical; arylalkylcarbonyl, in particular phenylacetyl and phenyl propionyl: arylcarbonyl, in particular benzoyl, optionally substituted with 1 to 3 groups from R6; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; fuifuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or phenylthiolcarbonyl, the phenyl itself optionally being substituted by 1 to 3 groups from R6; alkylthiolcarbonyl; haloalkylthiolcarbonyl; alkoxyalkylthiolcarbonyl; cyanoalkylthiolcarbonyl; benzylthiolcarbonyl; furfurylthiolcarbonyl; tetrahydrofurfurylthiolcarbonyl; thienylmethylthliolcarbonyl; pyridylmethylthiolcarbonyl; or arylsulfonyl or - a carbamnoyl radical optionally mono or disubstituted by: - an alkyl or haloalkyl group of 1 to 6 carbon atoms or - a cycloalkyl, alkenyl or alkynyl group of 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl group or cyanoalkyl of 2 to 6 carbon atoms or 26 2706455 - a phenyl optionally substituted with 1 to 3 R6 groups; - a sulfamoyl group optionally mono or disubstituted by: - an alkyl or haloalkyl group of 1 to 6 carbon atoms or - a cycloalkyl, alkenyl or alkynyl group of 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl or cynoalkyl group of 2 with 6 carbon atoms or - a phenyl optionally substituted with 1 to 3 R6 groups; - an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or cycloalkylsulfonyl of 3 to 7 carbon atoms; - R4 and R5 taken together can also form, with the nitrogen atom to which they are attached, an optionally substituted pyrrolidino, piperidino, morpholino or piperazino group by alkyl of 1 to 3 carbon atoms. -R6 represents: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical of 1 to 6 carbon atoms or - a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio radical of 3 to 6 carbon atoms or - the nitro or cyano group or - an amino radical optionally mono or disubstituted by an alkyl or acyl radical of 1 to 6 carbon atoms or alkoxycarbonyl of 2 to 6 carbon atoms - a phenyl or phenoxy radical or pyridyloxy, these radicals being optionally substituted; 27 2706455 and agriculturally acceptable salified forms of these compounds. 2. Optically active compounds according to claim 1 of formula II: N X N- (M) p - R3 R6- W N w N-R4 R5 3. Optically active compounds of formula II according to claim 2 in which W represents an oxygen atom. 4. Process for the preparation of the compounds of formula I in which p = 1 and M = S, and W = O, according to one of claims 1 to 3, by reaction of the compound of formula II: H 1- R2 N ^ S R '4 /' NOT W N-R4 R5 in which W represents an oxygen atom, with the compound of the formula R3X, in which X represents the chlorine, bromine or iodine atom or the sulfate group, or an alkylsulfonyloxy or arylsulfonyloxy group, alkyl and aryl being as defined above for R1 and R2; in a solvent and in the presence of a base, at a temperature of between -5 C and +80 0C. 28 2706455 5. Preparation process according to claim 4 characterized in that the solvent is chosen from ethers, cyclic ethers, alkyl esters, acetonitrile, alcohols of 1 to 3 carbon atoms, aromatic solvents, preferably tetrahydrofuran. 6. Preparation process according to claim 4 characterized in that the base is chosen from an alcoholate, preferably potassium tert-butoxide, an alkali or alkaline earth hydroxide, an alkali carbonate or a tertiary amine. 7. Process for the preparation of the compounds of formula I in which p = 1 and M = O, and W = O, according to one of claims 1 to 3, characterized in that the corresponding compound of formula I for which p = 1 and M = S is reacted with the alcohol of formula R3OH, in a solvent, in the presence of a strong base, and with a temperature between 50 and 80 C. 8. Preparation process according to claim 7, characterized in that the strong base is chosen from an alkali metal hydroxide, a strong organic base, or an alkali metal alcoholate of formula R30-Met. +, In which Met. + Represents a alkali or alkaline earth metal. 9. Preparation process according to claim 7 characterized in that the reaction is carried out by taking alcohol R3OH as solvent and as base sodium alcoholate R30-Na +. 10. Process for the preparation of the compounds of formula I in which p = 0 and R3 is a hydrogen atom, according to one of claims 1 to 3, by reaction of the compound of formula VII: 29 2706455 R2 NH2 R1 'N H NOT Y N-R4 R5 with an excess of the dimethylacetal of the dimethylformamide, at a temperature between 10 and 100 C. 11. Process for preparing the optically active compounds of formula I in which R3 is a C1-C2 alkyl radical, optionally halogenated, and in which p = 0 or p = 1 and M = CH2, according to one of claims 1 to 3, by reaction of the compound of formula IX: R2 N R3 R'i o with the compound of formula V: R4-N-NH2 I R5 12. Compounds useful in particular as intermediates in preparation of the compounds of formula I according to one of claims 1 to 3, characterized in that they have the formula: H I R2. N S R 'R21 R / N R1-C-N = C-S W N-R4 I I CO2R R5 III IV 2706455 R2 NH2 N. R2f <NH2 e Y N-R4 Rl CO2H I VI VII R R2 NH3 C1- R C1 ci or VIII in which R 1 to R 5 have the same meanings as in general formula I of the invention, and formula IX: R2 * N R3 R \ / 0 Gold IX in which R1 and R2 have the same meaning as above and R3 represents an optionally halogenated C1-C3 alkyl radical. 13. Fungicidal compositions comprising, in combination with one or more solid or liquid supports acceptable in agriculture and / or surfactants active ingredients also acceptable in agriculture, one (or more) active ingredient chosen from the compounds of formula I, according to one of claims 1 to 3. 14. Process for the treatment of cultures affected or liable to be affected by fungal diseases, characterized in that one applies, in a preventive or curative manner, an effective amount of an optically active compound of formula I, according to one of claims 1 to 3. F 31 2706455 15. A method of treating crops according to claim 18 characterized in that the compounds of formula I are applied at doses of 0.005 to 5 kg / ha, preferably 0.01 to 1 kg / ha.