HRP921456A2 - 2-imidazoline-5-one and 2-imidazoline-5-thiones derivatives as fungicides - Google Patents

Description

The presented invention relates to new imidazolinone and imidazolinthione compounds that are used for plant protection. It also refers to procedures for the preparation of those compounds and products that can be used as intermediates in the preparation procedures. Further, it refers to the use of these compounds as fungicides, fungicidal mixtures based on these compounds and methods for combating fungal diseases of plants using these compounds.

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

Another aim of the present invention is to propose compounds which have a scope of application also extended in the field of fungal diseases.

These goals were achieved by the products according to the invention, which are derivatives of 2-imidazolin-5-one and 2-imidazolin-5-thione of the general formula (I)

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where is:

-W atom of sulfur or oxygen or group S=O.

-A represents O or S

-n = 0 or 1

-B represents N(R5) or O or S or C(R5)(R6) or C=O.

-R1 and R2, equal or different, represent:

-F, provided the two groups are different from H, or

-alkyl or haloalkyl radical with 1 to 6 carbon atoms, or

-Alkoxyalkyl, alkynthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical with 2 to 6 carbon atoms, or

-dialkylaminoalkyl or cycloalkyl radical with 3 to 7 carbon atoms, or

-aryl radical, which includes phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolimyl, or methylene dioxyphenyl, optionally substituted with 1 or 3 groups selected from R7, or

-arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, where the terms aryl and alkyl are defined later, or

- R1 and R2 can form, with the carbon to which they are connected in the ring, one carbocycle or heterocycle, with 5 to 7 atoms, in which case they can be fused with some phenyl, possibly substituting 1 to 3 groups selected from R7,

-R3 represents:

- an alkyl group with 1 to 6 carbon atoms, or

- one alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cynoalkyl, thiocyanoalkyl, oxoalkyl, alkenyl or alkynyl group with 2 to 6 carbon atoms, or

-dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group with 3 to 6 carbon atoms, or

-one N,N-dialkylcarbamoylalkyl group with 4 to 8 atoms, or

- one arylalkyl group, where the alkyl part is a radical with 1 to 6 carbon atoms, while the aryl part is phenyl, naphthyl, thienyl, furyl, pyridyl, possibly substituted by 1 to a group selected from R7,

-R4 represents:

-a hydrogen atom when n is equal to 1, or

- one alkyl group with 1 to 6 carbon atoms, or

- one alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, alkenyl or alkynyl group with 2 to 6 carbon atoms, or

-dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group with 3 to 6 carbon atoms, or

-one N,N-dialkylcarbamoylalkyl group with 4 to 8 atoms, or

- some aryl radical, including phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, ozolinolinyl, or dioxyphenyl, optionally substituted by 1 to 3 groups selected from R7, or

-one arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, where the terms aryl and alkyl are defined later, or

- one amino group disubstituted by two groups, the same or different, chosen from:

- one alkyl radical with 1 to 6 carbon atoms,

- one alkoxyalkyl, alkenyl or alkynyl radical with 3 to 6 carbon atoms,

- one cycloalkyl radical with 3 to 7 carbon atoms,

- one arylalkyl radical, which will be determined later, phenyl or naphthyl optionally substituted 1 to 3 groups selected from R7, or

-one thienylmethyl or furfuryl radical

-one pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl with 1 to 3 carbon atoms,

-R5 represents:

-H, except when R 3 and R 4 are equal to H, or

-one alkyl, haloalkyl, alkylthioalkyl, alkyl, alkenyl, acyl, haloacyl,

Alkoxycarbonyl, Alloalkylsulfonyl, Alkoxyalkylsulfonyl, Cyanoalkylsulfonyl radical

with 2 to 6 carbon atoms, or

- one alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl radical

with 3 to 6 carbon atoms, or

-one formyl radical, or

-one cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbinyl,

an alkynylcarbonyl radical with 3 to 6 carbon atoms, or

-cycloalkylcarbonyl radical with 4 to 8 carbon atoms, or

- one phenyl radical; arylalkylcarbonyl, especially phenylacetyl and phenylpropionyl; arylcarbonyl,

especially benzoyl, possibly substituted by 1 to 3 groups from R7; thienylcarbonyl;

furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl;

tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl;

phenoxycarbonyl; or phenylthiocarbonyl, phenyl itself possibly substituted by 1 to 3 groups from

R7; alkylthiolcarbonyl, haloalkylthiolcarbonyl; alkoxyalkylthiolcarbonyl; cyanoalkylthiolcarbonyl;

benzylthiolcarbonyl; furfurylthiolcarbonyl; tetrahydrofurfurylthiolcarbonyl;

thienylmethylthiolcarbonyl; pyridylmethylthiolcarbonyl; or arylsulfonyl, or

- one carbamoyl radical, possibly mono- or disubstituted

- one alkyl or haloalkyl group with 1 to 6 carbon atoms, or - one cycloalkyl, alkenyl or alkynyl group with 3 to 6 carbon atoms, - one alkoxyalkyl, alkylthioalkyl or cyanoalkyl group with 2 to 6 carbon atoms, or

-one phenyl, possibly substituted by 1 or 3 groups R7,

-one sulfamoyl group, possibly mono- or disubstituted

- one alkyl or haloalkyl group with 1 to 6 carbon atoms, or - one cycloalkyl, alkenyl or alkynyl group with 3 to 6 carbon atoms, - one alkoxyalkyl, alkylthioalkyl or cynoalkyl group with 2 to 6

carbon atoms,

-one phenyl optionally substituted with 1 or 3 R7 groups,

- one alkylthioalkylsulfonyl group with 3 to 8 carbon atoms or cycloalkylsulfonyl

group with 3 to 7 carbon atoms,

-R6 represents:

-hydrogen atom or

-cyano group, or

- one alkyl group with 1 to 6 carbon atoms or a cycloalkyl group with 3 to 7 carbon atoms, or

- one acyl or alkoxycarbonyl group with 2 to 6 carbon atoms or

-benzoyl group possibly substituted by 1 to 3 groups R7,

-R7 represents:

-one atom of a halogen, or

-one alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical with 1 to 6 carbon atoms, or

-one cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio radical with 3 to 6 carbon atoms, or

-one nitro or cyano group, or

- one amino radical, possibly mono- or disubstituted by one alkyl or acyl radical with 2 to 6 carbon atoms,

- one phenyl, phenoxy or pyridyloxy radical, where these radicals are optionally substituted;

as well as their salts.

Certain compounds of formula Ia are known as particular embodiments of formula I

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in which W, R 1 to R 6 have the same meaning as in formula I.

Compounds such as S-alkyl derivatives 5,5-diphenyl-2-thiohydantoin and 5,5,-diphenyl dithiohydantoin have been specially studied for their pharmacological properties:

a) Zejc, A.; Dissertations Pharmaceuticae et Pharmacologicae, 20(5), 507-524 and 525-537 (1968)

b) Lucka-Sobstel, B.; Dissertations Pharmaceuticae et Pharmacologicae, 22(1), 13-19 (1970)

c) Fetter, J.; Harsanyi, K.; Nyitrai, J.; Lempert, K.; Acta Chemica (Budapest), 78(3), 325-333 (1973).

No fungicidal activity has been described for these compounds.

Other compounds forming particular embodiments of formula I are described by Bohme, Martin and Strahl in Pharmazie 313 10-15(1980) (ref d).

These are the following 3 connections:

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These compounds are included in the compounds of formula Ib, which form part of the invention

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wherein W and R1 to R5 have the same meanings as in formula I.

Compounds of formula Ia can be prepared according to known procedures described in the above-mentioned literature, as well as in the following:

e) Blitz, H.; Chemische Berichte 42, 1792-1801 (1909)

f) Chattelain, M. and Cabrier, P.; Bulletin de la Societe Chimique de France 14(1947), 639-642

g) Carrington C.H.; Warring, W.S.; Journal of Chemical Society (1950) 354-363 h) Lampert, K.; Breuer, J.; Lemper-Streter, M.; Chemische Berichte 92,235-239 (1959).

i) Shalaby, A.; Daboun, H.A.; Journal fur Praktische Chemie; 313(6), 1031-1038 (1971)

j) Simig, G.; Lemper, K.; Tamas, J.; Tetrahedron 29(33), 3571-3578 (1973)

k) Schmidt, U.; Heimgartner, H.; Schmidt, H.; Helvetica Chemica Acta 62(1979), 160-170

1) Muraoka, M.; Journal of Chemical Society Perkin Transaction I, (1990), 3003-3007 or according to procedures A, B, C or D which will be described later.

Compounds of formula lb can be prepared according to the procedure described by Bohme, Martin and Strahl in Pharmazie 313 10-15(1980) (under d) or according to one of the procedures that will be described in the following text.

Process A: Process for the preparation of compounds of formula (I)

Compounds of formula (I) are prepared by S-alkylation of 2-thiohydantoin (II) according to the following reaction:

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where X represents a chlorine, bromine or iodine atom, or a sulfate group, or an alkylsulfonyloxy or arylsulfonyloxy group, where alkyl and aryl are as described above for R1 and R2. An alcoholate, for example potassium tert-butylate, an alkaline hydroxide or an alkaline earth hydroxide, an alkaline carbonate or a tertiary amine can be used as the alkali. Ethers, cyclic ethers, alkyl esters, acetonitrile, alcohols with 1 to 3 carbon atoms, aromatic solvents, for example tetrahydrofuran, at temperatures between -5°C and -80°C can be used as solvents.

This procedure is suitable for compounds in which W represents a sulfur or oxygen atom.

2-Thiohydantoins of formula (II) can be prepared according to the procedures described in the literature, such as, for example, in the following works:

e) Blitz, H.; Chemische Berichte 42, 1792-1801 (1909)

n) Eberly and Dains; Journal of the American Chemical Society, 58(1936), 2544-2547

0) Carrington, C.H.; Journal of Chemical Society (1947) 681-686

g) Carrington C.H.; Warring, W.S.; Journal of the Chemical Society (1950) 354-363

h) Lampert, K.; Breuer, J.; Lemper-Streter, M.; Chemische Berichte 92, 235-239 (1959)

1) Koltai, R; Nyitrai, J.; Lempert, K.; Burics, L.; Chemische Berichte 104, 290-300(1971)

or according to procedure E or F which are described herein and form part of the invention.

Procedure B: Preparation of compounds Ic.

Preparation of 2-methylthio-2-imidazolin-5-one of formula (Ic) for cyclization of iminodithiocarbonate of formula (V) is carried out according to the general scheme:

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a) Iminodithiocarbonates (III) can be prepared according to the conditions described in the literature for analogous compounds:

-CAlvarez Ibara et al.: Tetrahedron Letters, 26(2), 243-246 (1985)

- E. Melendez and others; Synthesis 1981,961 according to :

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b) Compounds of formula (V) are prepared by condensation of compounds of formula (III) with amines or hydrazines of formula (IV). In order to carry out the condensation, the acid (III) must be activated as an acid chloride, dicyclohexylsulfate with the addition of dicyclohexylcarbodiimide, or diimidazolide with the addition of carbonyldiimidazole. Condensation is carried out under conditions that are common for this type of reaction.

c) Cyclization of compounds (V) is carried out by simple heating in an aromatic solvent with reflux. Xylene, chlorobenzene or dichlorobenzene are especially used as solvents.

Procedures C: Derivation of compounds (Ib') and (Id')

Procedure: C1: Preparation of compound Ib by derivatization of compound Ib'

Compounds of formula (Ib') [compounds (Ib) in which R5 is a hydrogen atom] can be alkyls, acyls, alkoxycarbonyls, carbamoyls or sulfamoyls according to the following general scheme:

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R 5 herein represents an alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, carbamoyl or sulfamoyl group, such as will be defined later.

X represents some halogen, sulfate group or some phenoxy, possibly substituted, or one alkylsulfonyloxy or arylsulfonyloxy group, or one R5 group, where R5 is acyclic.

Alkaline hydrides, alcoholates or a tertiary amine can be used as alkali. The reaction is carried out at a temperature between -30°C and +50°C. As a solvent, for example, ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents can be used.

Carbamoylation of compound (Ib) can be carried out by reaction with isocyanates or isothiocyanates according to the scheme:

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The reaction is carried out under the same conditions as described above, where the aforementioned alkali is used in catalytic amounts.

Procedure C2: Preparation of compound Id.

Compounds Id' (compounds Id where R2 is a hydrogen atom) can be alkyl at position 4 according to the scheme:

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X represents one chlorine, bromine or iodine atom. An alcoholate, a metal hydride or an amidate can be used as an alkali. The reaction can be carried out at temperatures between -30°C and +80°C. Ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents can be used as solvents.

Procedure D: Preparation of the S-oxide derivative of 2-imidazolin-5-thione

Compounds of formula (I) in which W represents the S=O group, are prepared by oxidation of 2-imidazolin-5-thione according to the scheme

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Peroxides, especially per.acids, can be used as oxidants. The oxidant should be used in a stoichiometric amount. Oxidation is carried out in chloroform or methylene chloride at a temperature between -20°C and +20°C.

Procedure E: Preparation of dithiohydantoin of formula (VI)

Dihydantoins of formula (VI) can be prepared by capturing the alpha anion of isothiocyanates with isocyanates that can be ionized according to the scheme:

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At least one of the groups R1 or R2 must be electron-withdrawing (aryl, substituted aryl, alkoxycarbonyl...). R4-NCS isocyanates must not bind to the anode; aryl isothiocyanates are particularly suitable for this reaction.

Potassium tert-butylate, lithium or sodium bis(trimethylsilyl)amidate, alkali hydrides can be used as alkali. Ethers, cyclic ethers can be used as solvents. The reaction is carried out at a temperature lower than -60 °C. The anion is collected gradually as it is formed. For this reason, it is cooled with mixtures of 2 isocyanates on molten alkali at a temperature lower than -60°C.

Process F: Preparation of 2-thiohydantoin of formula (VII)

Preparation of 2-thiohydantoin (VII) starting from isocyanate derivatives of amino acids (VIII) is carried out according to the reaction:

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Cyclization can be achieved in two ways:

- by heat: in this case, the mixture of reactants is heated at a temperature between 110°C and 180°C in an aromatic solvent such as toluene, xylene, chlorobenzenes,

- in alkaline: the process takes place in the presence of some equivalent of one alkali such as alkaline alcoholate, alkaline hydroxide or a tertiary amine. Under these conditions, cyclization occurs at temperatures between -10°C and -80°C. Ethers, cyclic ethers, alcohols, esters, DMF, DMSO ... can be used as solvents.

Isocyanates can be prepared according to a procedure outlined in Sulfur Reports Volume 8 (3) pages 327-375 (1989).

Procedure G: Preparation of compounds of formula I in one step

During the cyclization of 2-thiohydantoin according to process F, if it is carried out in an alkaline medium, at the end of the reaction thiohydantoin is obtained as a thiolate which can directly react with one alkyl halide or sulfate R3X or with R3X where X is one alkylsulfonyloxy or one arylsulfonyloxy to form (AND).

Procedures A and F are connected via the scheme:

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Process H: Preparation of compounds of formula Ia, where (B)n is a sulfur atom These compounds can be prepared by reacting one sulfuryl chloride R4SCI with one imidazoline of formula IX according to the scheme:

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The reaction is carried out at a temperature between -20°C and +30°C in the presence of a molar equivalent of some alkali. Alkaline hydrides, alkaline alcoholates or tertiary amines can be used as alkali. Polar solvents such as ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, or aromatic solvents can be used as solvents. Imidazolinones (IX) can be prepared by procedures analogous to procedure A.

Compounds that are recommended due to their increased fungicidal activity and/or due to their easy synthesis are:

1) Compounds of formula lb,

2) Compounds of formula I, especially lb, where R5 is a hydrogen atom,

3) Compounds where R1 and R2 are different from H,

4) Compounds where R2 represents one alkyl group with 1 to 3 carbon atoms,

5) Compounds where Rl represents cyclic phenyl, optionally substituted with R7,

6) Compounds where R3 represents an alkyl group with 1 to 3 carbon atoms,

7) Compounds where R4 represents cyclic phenyl, optionally substituted with R7,

8) Compounds in which R3 represents a methyl group.

The following examples are given as an illustration of the compounds according to the invention, their methods of preparation and their antifungal properties.

The structure of all products was determined by at least one of the following spectroscopic techniques: 1H NMR and 13C NMR spectrometry, infrared spectrometry and mass spectrometry.

In the following tables, methyl and phenyl radicals are marked with Me and Ph, and Cte indicates a physical constant that can be the melting point (PF) or the refractive index (nD20).

Example 1: Preparation of compound no. 34 according to procedure A

Dissolve 0.9 g (3 mmol) of 3-benzyl-5-methylphenyl-2-thiohydantoin in 30 mL of anhydrous tetrahydrofuran. The mixture is cooled to 0°C and 0.34 g (3 mmol) of potassium tert-butylate is added. The reaction is left for 10 min at 0°C, after which 0.46 g (3.3 mmol) of methyl iodide is added dropwise at that temperature; precipitation of potassium iodide is observed. Allow the mixture to reach room temperature. The mixture is diluted with 100 mL of ethyl acetate. The solution is washed twice with 100 mL of water each. The solution is dried over sodium sulfate and treated with activated carbon. Concentration of the solution is carried out under reduced pressure, and 0.6 g of 1-benzyl-4-methyl-2-methylthio-4-phenyl-2-imidazolin-5-one (compound no. 34) is obtained as a light yellow solid which melts at 68°C.

The compounds described below were prepared in the same way:

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The following are prepared in the same way:

- 4-(3-pyridyl)-4-methyl-1-(N-phenylamino)-2-methylthio-2-imidazolin-5-one (compound 51: PF 156°C)

- 4-phenyl-4-methyl-1-(benzyloxy)-2-methylthio-2-imidazolin-5-one (compound 56: honey)

Example 2: Preparation of compound no. 7 according to procedure B

a) N-[bis(methylthio)methylene]-2-phenyl glycine (compound (III) with R1= phenyl and R2= H):

100 g (0.66 mol) of phenylglycine is dissolved in 335 g (1.3 mol) of a 22% aqueous solution of potassium carbonate at +5°C. 55.3 g of carbon disulfide are added and everything is mixed well: a precipitate appears and the mixture acquires an orange color. The reaction is left for 3 hours at room temperature, then 103 g (0.73 mol) of methyl iodide is added, while the temperature of the mixture is maintained below 30°C. The reaction is left for 0.5 hours, then 74 g (0.66 mol) of a 50% potassium carbonate solution is added. The reaction is left for 0.5 hours, then another 103 g of methyl iodide is added and left for 1 hour. The mixture is diluted with 300 mL of water. It is acidified to pH = 4 with 1N hydrochloric acid. The product is extracted with 500 mL of ethyl acetate. the solution is dried over magnesium sulfate and then concentrated under reduced pressure. 49.5 g of N-[bis(methylthio)methylene]-2-phenyl glycine are obtained (yield 31%) as a yellow solid melting at 112°C.

b) {N-[bis(methylthio)methylene]-2-phenylglycine}metachlorophenyl-hydrazide (compound V with R1 = phenyl, R2 = H, R4 = metachlorophenyl, n = 1, B- NH):

38.8 g (16.4 mmol) of dicyclohexylcarbodiimide was added to a solution of 2.95 g (16.4 mmol) of N-[bis(methylthio)methylene]-2-phenylglycine in methyl chloride (40 mL), and the reaction was leave for 0.5 hours at room temperature. 2.34 g (16.4 mmol) of metachlorophenylhydrazine are added. It is heated for 0.5 hours at 30°C. The insoluble ingredients are filtered. The filtrate is washed with 2 x 30 mL of water. The solution is concentrated: an oil is obtained which is purified by chromatography on a silica column. After cleaning, 2.5 g of {N-[bis(methylthio)methylene]-2-phenylglycine}metachlorophenylhydrazide is obtained as a pink powder melting at 146°C.

c) 1-metachlorophenyl-2-methylthio-4-phenyl-2-imidazolin-5-one (compound no. 7)

Dissolve 1.92 g (5 mol) of {N-[bis(methylthio)methylene]-2-phenylglycine}metachlorophenylhydrazide in 30 mL of xylene. The reaction mixture is heated for 4 hours under reflux. The mixture is concentrated under reduced pressure. The resulting mixture is triturated with 10 mL of ether: the product crystallizes. The precipitate is filtered, the product is dried in a vacuum desiccator. Again, in a yield of 56%, compound no. 7 as a yellow powder melting at 196°C.

Working similarly, the compounds appearing in the following table were prepared:

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Example 3: Preparation of 4-methyl-1-(N-methyl-N-phenylamino)-2-methylthio-4-phenyl-2-imidazolin-5-one (compound no. 22) by alkylation (methylation) according to procedure C1

In a solution of 4-methyl-1-phenylamino-2-methylthio-4-phenyl-2-imidazolin-5-one (compound no. 9) (1 g; 3.2 mmol) in anhydrous tetrahydrofuran (30 mL), precooled at 0°C, 0.4 g (3.5 mmol) of potassium tert-butylate was added. The reaction takes 0.5 hours. 0.5 g (3.5 mmol) of methyl iodide was added and the reaction was left for 0.5 hours at room temperature. The reaction mixture is poured into 100 mL of water and the product is extracted with 100 mL of diethyl ether. The solution in ether was dried over magnesium sulfate and then concentrated. The product was crystallized after trituration with 10 mL of diisopropyl ether. It was filtered and then dried in a vacuum. 0.73 g (yield: 70%) of compound no. 22 as a light yellow powder melting at 124°C

Example 4: Preparation of 4-methyl-1-(N-acetyl-N-phenylamino)-2-methylthio-4-phenyl-2-imidazolin-5-one (compound no. 23) by acylation (acetylation) according to procedure C1

In a solution of 4-methyl-1-phenylamino-2-methylthio-4-phenyl-2-imidazolin-5-one (compound no. 9) (1 g; 3.2 mmol) in anhydrous tetrahydrofuran (30 mL), precooled at 0°C, 0.4 g (3.5 mmol) of potassium tert-butylate is poured in. The reaction takes 0.5 hours at 0°C. Then 0.25 g (3.5 mmol) of acetyl chloride was added and left for 0.5 hours at room temperature. The reaction mixture is poured into 100 mL of water and extracted with 100 mL of diethyl ether. The ethereal solution is washed with water until neutral. It is dried on magnesium sulfate, then concentrated. An oil is obtained which is purified by chromatography on a silica column. The purified product crystallizes from diisopropyl ether. 0.25 g of compound no. 23 as a white powder that melts at 132°C.

In the same way, compounds no. 39 and 42.

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Example 5: Preparation of 4-ethyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound 48) according to procedure C2

To a solution of 1.5 g (5.05 mmol) of 2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound no. 5) in 50 mL of anhydrous tetrahydrofuran, add 0.55 g of potassium -tert-butylate. The reaction proceeds for 30 min at room temperature, then 0.8 g (5.05 mmol) of ethyl iodide is added. The reaction is left for 1 hour at room temperature. The mixture is diluted with 150 mL of ethyl acetate. The solution is washed with water and concentrated under reduced pressure. The product is purified by chromatography on a silica column (silica Merck 60H; eluent: ethyl acetate 25%/heptane 75%). 0.65 g of compound no. 48 as a yellow-brown powder melting at 147°C

Proceeding in the same way, compound no. 49.

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4-methyl-2-methylthio-4-(4-fluorophenyl)-1-phenylamino-2-imidazolin-5-one (compound 68) was prepared in the same way.

Example 6: Preparation of compound 2 according to procedure D

Dissolve 1.7 g (5.2 mmol) of 4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound no. 1) in 20 mL of chloroform. The solution is cooled to -10°C and a solution of 1.35 g (5.5 mmol) of m-chloroperbenzoic acid and 30 mL of chloroform is added over 10 minutes. After addition, the temperature is allowed to reach room temperature. The mixture is washed with saturated aqueous sodium bicarbonate solution and then with distilled water. The organic phase is treated with activated carbon and then concentrated. The obtained oil is treated with 20 mL of ether: the oil melts and a dark yellow precipitate forms. The precipitate is filtered. The product is dried in a vacuum. 0.4 g (yield: 25%) of compound no. 2 as a dark yellow powder that melts at 150°C.

No. R2 R3 R4 R5 W Cte

2 Me Me Ph H S=O PF= 150°C

Example 7: Preparation of 3,5-diphenyl-5-methyl-ditohydantoin according to procedure E

In a closed 500 mL glass flask, in an atmosphere of dry argon, dissolve 15.1 g (122 mmol) of potassium tert-butylate in 200 mL of tetrahydrofuran. The solution is cooled to -70°C. A solution of 20 g (122 mmol) of α-methylbenzylisothiocyanate, 16.55 g (122 mmol) of phenylisothiocyanate and 50 mL of tetrahydrofuran is added dropwise, while maintaining the temperature of the mixture below -60°C. After the addition, the mixture is kept at -70 °C for 0.5 hours, then allowed to reach room temperature. The mixture is washed in 500 mL of water. It is acidified to pH = 1 with the addition of N hydrochloric acid. The product is extracted with ethyl acetate (2x 150 mL). The solution is dried over magnesium sulfate. It concentrates at reduced pressure. The product crystallizes from 50 mL of ether. The precipitate is filtered. 21 g (yield: 58%) of 3,5-diphenyl-5-methyl-ditohydantoin, a yellow powder melting at 157°C, is obtained.

Example 8: Preparation of 3,5-diphenyl-5-methyl-ditohydantoin according to procedure F

Dissolve 4.7 g (20 mmol) of ethyl 2-isothiocyanate-2-phenylpropionate in 40 mL of xylene.

2.15 g (20 mmol) of phenylhydrazine were added and refluxed for 4 hours. Cool to room temperature with the formation of a dark yellow precipitate. The precipitate is filtered, washed with 5 mL of diisopropylether and dried under vacuum. 4.5 g (yield: 77%) of 3,5-diphenyl-5-methyl-ditohydantoin are obtained as a dark yellow powder melting at 164°C.

Example 9: Preparation of 5-methyl-5-phenyl-3-(2-pyridylamino)-2-thiohydantoin according to procedure F

Dissolve 2 g (9 mmol) of methyl-2-isocyanato-2-phenyl-propionate in 30 mL of tetrahydrofuran. A solution of 0.99 g of 2-hydrazinepyridine and 10 mL of tetrahydrofuran is added: the temperature of the mixture rises from 20 to 30°C and a solid is formed. The reaction is left for 0.5 hours at 30°C, then cooled to 5°C. A solution of 1 g of potassium tert-butylate and 10 mL of tetrahydrofuran is added: the mixture acquires a purple color. The reaction is left at room temperature for 2 hours. The mixture is washed with 150 mL of water. The mixture is neutralized with acetic acid. The product is extracted with 150 mL of ethyl acetate. The solution is washed with water, dried on magnesium sulfate and treated with activated carbon. It is concentrated and then the product is crystallized in 20 mL of ether. The precipitate is filtered and then dried under vacuum. 1.6 g (yield: 60%) of 5-methyl-5-phenyl-3-(2-pyridylamino)-2-thiohydantoin are obtained, a light yellow solid melting at 80°C.

According to this procedure, compounds of formula (VII), intermediate products of compounds of formula I, marked with initial number 1001, were prepared, shown in the following table:

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[image]

Example 10: Preparation of compound 9 according to procedure G

11.1 g (50 mmol) of methyl-(2-isothiocyanate-2-phenyl)propionate are dissolved in 150 mL of anhydrous tetrahydrofuran. Gradually, over 10 minutes, a solution of 5.4 g (50 mmol) of phenylhydrazine and 50 mL of anhydrous tetrahydrofuran is added: the temperature of the mixture rises to 35°C. After addition, the reaction proceeds for 0.5 hours at 30°C. so the mixture is cooled to -5°C. At this temperature, a solution of 5.6 g (50 mmol) of potassium tert-butylate and 50 mL of anhydrous tetrahydrofuran is added: the mixture acquires a purple color and a precipitate forms. Leave at 0°C for 0.5 hours, then add 8.5 g (60 mmol) of methyl iodide. Leave for 1 hour at room temperature. The mixture is diluted with 200 mL of ethyl acetate. The mixture is washed twice with 150 mL of water each. The solution is dried on magnesium sulfate, then treated with activated carbon. It is concentrated: a dark purple oil is obtained which crystallizes in 50 mL of ether. The precipitate is washed and dried in a vacuum. The second part of the product is obtained after evaporation of pure water and represents the residue as an oil with 50 mL of diisopropyl ether. 12 g (yield: 77%) of 4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound 9) are obtained as a dark yellow powder melting at 149°C.

Working in the manner described above, the following compounds are prepared:

[image]

[image]

Example 11: Preparation of 3-phenyl-4-methyl-1-(phenylthio)-2-methylthio-2-imidazolin-5-one (compound 95: melting point 112°C)

0.6 g (2.7 mmol) of 2-methylthio-4-methyl-4-phenyl-2-imidazolin-5-one with 50 mL of anhydrous tetrahydrofuran (THF) are placed in a 100 mL vessel with an inert atmosphere. It is mixed on a magnetic stirrer and cooled to 0°C (ice bath + acetone). 0.30 g (1 molar equivalent) of potassium tert-butylate was added and stirred for 10 minutes at 0°C. Then a solution of 0.40 g of phenylsulfenyl chlorate and 10 mL of anhydrous THF is poured in. Let it reach room temperature for 1 hour. The reaction mixture is poured into 100 mL of water. It is extracted with 100 mL of ethyl acetate. The organic part is washed 4 times with water and dried over sodium sulfate. 1 The organic part is evaporated in a vacuum. A yellow oil is obtained which crystallizes in diisopropylether after purification on silica, with a yield of 68% (melting point: 112°C).

Example 12: in vitro testing

The effect of the compound according to the invention on fungi that cause diseases of cereals and other plants was tested:

Fusarium oxysporum f.sp.melonis

Rhizoctonia solani AG4

Helminthosporium gramineum

Pseudocecrosporella herpotricoides

Alternaria alternata

Septoriae nodorum

Fusarium roseum

Pythium rostratum

Pythium vexans

The procedure for each experiment is as follows: the nutrient medium, which consists of potatoes, glucose and agar-agar (PDA mixture), is placed in a liquid state in a series of Petri dishes (100 mL per dish) after sterilization in an autoclave at 120°C .

During the filling of the bowls, a solution of the active substance in acetone is injected into the liquid mixture in order to obtain the desired final concentration.

For comparison, Petri dishes analogous to the previous ones are used, in which the same amount of nutrient medium is poured, but which does not contain an active substance.

After 24 hours, one piece of shredded mycelium with one culture of each fungus is planted in each bowl.

The bowls were kept for 5 days at 20°C, so the development of fungi in the bowls that contained the active substance being tested was compared with the development of the same fungi in the bowls that were used as a benchmark.

For each tested compound, the degree of fungal suppression was determined for a dose of 20 ppm.

The following results were obtained:

A good effect is the degree of suppression of fungi, which is 80% and 100%, and is valid for:

-compounds 9, 13, 16, 22, 26 and 34 for Pythium rostratum and Pythium vexans.

- compound 26 for Fusarium oxysporum and Fusarium roseum

- compounds 11, 16, 22 and 26 for Alternaria alternata,

-compounds 11, 16 and 26 for Rhisoctonia solani.

- compounds 16 and 26 for Pseudocercosporelle herpotrichoides,

- compounds 11, 16 and 26 for Septoria nodorum.

- compounds 9, 11, 16 and 26 for Helminthosporium gramineum.

Example 13: In vivo test on Plasmopara viticola

An aqueous suspension of the active substance to be tested is prepared by fine grinding, which has the following composition:

- active substance: 60 mg

- surfactant Tween 80 (oleate derivative of polyethoxyethylene sorbitan) in a 10% solution in water: 0.3 mL

- top up with water up to 60 mL.

This aqueous suspension is diluted with water to obtain the desired amount of active substance.

Vine seedlings (Vitis vinifera), of the Chardonnay variety, were grown in cups. All plants were two months old (the stage when they have 8 to 10 leaves, height 10 to 15 cm), and were treated by spraying with the aforementioned water suspension.

The plants used for comparison were treated with an aqueous solution that did not contain the active substance.

After 24 hours of drying, each of the plants was infected by spraying with an aqueous suspension of Plasmopara viticola spores obtained starting from a 4-5 day old culture, which was suspended in a ratio of 100,000 units per cm3.

Infected plants were then incubated for two days at about 18°C in a moisture-saturated atmosphere, and then for 5 days at about 20-22°C at a relative humidity of 90-100%.

The check was carried out 7 days after infection, by comparison with reference plants.

Under these conditions, it is observed that a dose of 1 g/L provides good protection (at least 75%) as a whole with the following compounds: 1, 2, 9, 10, 12, 13, 15, 16, 18, 20, 22, 23, 24, 25, 30, 31, 34, 35, 37, 39 to 43, 45, 48, 55 to 58, 60, 62, 64, 68, 73, 75, 76, 83 to 85, 88 to 91, 93 to 98, 101 to 108.

Example 14: In vivo test for Puccinia recondita

by finely grinding, an aqueous suspension of the active substance is prepared, which is tested with the following composition:

- active substance: 60 mg

- surfactant Tween 80 (oleate derivative of polyethoxyethylene sorbitan) in a 10% solution in water: 0.3 mL

- top up with water up to 60 mL.

This aqueous suspension is diluted with water to obtain the desired amount of active substance.

Grain in cups, sown on a substrate of peat and diatomaceous earth 50/50, at the stage when it reached a height of 10 cm, was treated by spraying with the specified suspension.

After 24 hours, an aqueous spore suspension (100,000 spores per cm3) was sprayed on the grain. This suspension is obtained from infected plants. The grain is placed in an incubation cell for 24 hours at around 20 °C and 100% relative humidity, after which another 7 to 14 days at 60% relative humidity.

Control of the condition of the plants is carried out between the 8th and 15th day after infection by comparing it with an untreated sample.

Under these conditions, it is noted that a dose of 1 g/L provides good protection (at least 75%) as a whole with the following compounds: 2, 9, 10, 15, 18, 20 to 22, 39, 55, 57, 64, 68, 75, 83 to 85, 88 to 90, 93, 94, 98.

Example 15: In vivo test on Phytophthora infestans

An aqueous suspension of the active substance is prepared by fine grinding, which is tested with the following composition:

- active substance: 60 mg

- surfactant Tween 80 (oleate derivative of polyethoxyethylene sorbitan) in a 10% solution in water: 0.3 mL

- top up with water up to 60 mL.

This aqueous suspension is diluted with water to obtain the desired amount of active substance.

Tomato seedlings (Marmande type) are grown in cups. After the plants were one month old (state with 5 to 6 leaves, height 12 to 15 cm), they were treated by spraying with the aforementioned aqueous suspension and at different concentrations of the compound being tested.

After 24 hours, each of the plants was infected by spraying with one aqueous spore suspension (30,000 spores per cm3) of Phytophtora infestans.

After this contamination, the tomato seedlings were incubated for 7 days, at about 20°C in an atmosphere saturated with moisture.

Seven days after they were infected, the results obtained in the case of plants treated with the active substance being tested were compared with those obtained in the case of plants used as an example for comparison. Under these conditions, it is noted that a dose of 1 g/L provides good protection (at least 75%) as a whole with the following compounds: 2, 9, 10, 30, 39, 45, 55, 68, 75, 84, 85, 90, 94, 98, 107, 108.

These results clearly show the good fungicidal properties of the derivatives according to the invention against fungal plant diseases that cause them from very different genera, such as Phycomycete, Basidiomycete, Ascomycete, Adelomycete or fungi imperfecti, especially Plasmopara viticola, Puccinia recondita and Phytophthora infestans.

In practical use, compounds according to the invention are rarely used alone. Most often, these compounds form part of the composition. These compositions, which can be used as fungicidal agents, contain as an active substance a compound according to the invention such as those described above, mixed with solid or liquid carriers, acceptable in agriculture, as well as surface-active agents acceptable in agriculture, in particular they can be used inert and common carriers and common surfactants. These compositions are also part of the invention.

These compositions can contain all kinds of other ingredients such as, for example, protective colloids, adhesives, coagulants, thixotropic agents, penetrating agents, stabilizers, chelates, etc. Most often, the compounds used according to the invention can be combined with any solid or liquid additives that correspond to the usual technologies for the preparation of preparations.

Generally speaking, compositions according to this invention usually contain about 0.05 to 95% (by weight) of a compound according to the invention (hereinafter: active substance), one or more solid or liquid carriers and, optionally, one or more surface-active agents.

By the term "carrier", in this description is meant some substance, organic or inorganic, natural or synthetic, with which the compound is combined to facilitate its application to plants, to seeds or to soil. These carriers are usually inert and must be acceptable for agriculture, especially for cultivated plants. Leg carriers should be solid (clays, silicates, natural or synthetic, silicon dioxide, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, especially butanol, etc.).

Surface-active agents can be emulsifying, dispersing or wetting agents, ionic or non-ionic, or a mixture of these surface-active agents. Examples include salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenosulfonic acid or naphthalene sulfonic acid, polycondensates of ethylene oxide with fatty alcohols, or fatty acids or fatty amines, substituted phenols (especially alkyl phenols or arylphenols), ester salts of sulfosuccinic acid, derivatives taurine (especially alkyltaurates), phosphorous esters of alcohol or polyoxyethylphenol, esters of fatty acids and polyvalent alcohols, functional derivatives of sulfates, sulfonates, and phosphates of the aforementioned compounds. The presence of at least one surface-active agent is usually necessary if the compound and/or the inert carrier are not soluble in water and when the carrier agent is water when applied.

Therefore, compositions according to the invention for use in agriculture can contain active substances according to the invention within very wide limits, even from 0.05% to 95% (by mass). It is suitable for the proportion of surface-active agents to be between 5% and 40% by mass.

These compositions according to the invention appear in very different forms, solid and liquid.

As forms of solid compositions, powders for dusting (the proportion of the compound can be up to 100%) and granules, especially those obtained by printing, pressing, impregnating a granular carrier, granulation of a powder (the proportion of the compound in such granules is between 0.5 and 80% in the last mentioned case), compresses or effervescent tablets.

The compounds of formula I can also be used as dusting powders. A composition containing 50 g of active substance and 950 g of talc can be used. A composition containing 20 g of active substance, 10 g of finely ground silicon dioxide and 970 g of talc can also be used. These ingredients are mixed and crushed and the mixture is used for dusting.

As forms of liquid compositions, or compositions that should be liquid when applied, solutions, especially water-soluble concentrates, emulsifying concentrates, emulsions, concentrated suspensions, aerosols, dissolvable powders (or dusting powders, creams, gels) can be mentioned .

Emulsifying or dissolving concentrates usually contain 10 to 80% of the active substance, while emulsions or ready-to-use solutions contain, as needed, 0.001 to 20% of the active substance.

In addition to the solvent, the emulsifiable concentrates can contain, if necessary, 2 to 20% of suitable additives, such as stabilizers, surface-active agents, penetrating agents, corrosion inhibitors, paints or the aforementioned adhesives.

Starting from these concentrates, emulsions of all desired concentrations are obtained by diluting them with water, which meet the special requirements for application to plants.

As an example, the composition of several concentrates that can emulsify is given:

Example of CE 1:

- active substance 400 g/L

-alkaline dodecylbenzene sulfonate 24 g/L

-nonylphenol-oxyethyl with 10 molecules of ethylene oxide 16 g/L

- cyclohexanone 200 g/L

- aromatic solvent refill up to 1 L

According to another formula of a concentrate that can emulsify, it is used:

Example of CE 2:

- active substance 250 g

- epoxidized vegetable oil 25 g

a mixture of alkylaryl sulfonate and

ether of polyglycol and fatty alcohols 100 g

-dimethylformamide 50 g

-xylene 575 g

Concentrated suspensions, which can also be used for dusting, are prepared to obtain a stable liquid product that does not form a precipitate, and which usually contains 10 to 75% of the active substance, 0.5 to 15% of surface-active agents, 0 ,1 to 10% of thixotropic agents, 0 to 10% of suitable additives, such as anti-foaming agents, corrosion inhibitors, stabilizers, penetration agents and adhesives, and, as a carrier, water or some organic liquid in which the active substance is poorly soluble, or insoluble: some organic solids or inorganic salts can be dissolved in the carrier to prevent precipitation or as antigels for water.

As an example, the composition of a concentrated suspension is given:

Example SC 1:

- active substance 500 g

- tristyrenephenol-polyethoxyl phosphate 50 g

-alkylphenol-polyethoxyl 50 g

- sodium polycarboxylate 20 g

- ethylene glycol 50 g

-organopolysiloxane oil (anti-foaming 1g

-polysaccharide 1.5 g

- water 316.5 g

Freezing powders (or dusting powders) are usually prepared to contain 20 to 95% of the active substance, and usually contain, in addition to the solid carrier, 0 to 30% of some antifoaming agent, from 3 to 20% of some dispersing agent , and, if necessary, 0.1 to 10% of one or more stabilizers and/or other additives, such as penetrating agents, adhesives, or anti-caking agents, colors, etc.

For the preparation of dusting powders or dissolving powders, the active substances are thoroughly mixed in a suitable mixer with additional substances and ground in a suitable mill or other suitable comminution machine. Powders with suitable solubility and the ability to form suspensions are obtained. A suspension of any concentration can be obtained with water, and these suspensions can be used very conveniently, especially for application to plant leaves.

Instead of powders, creams can be prepared. The conditions and methods of preparation and application are similar to those for soluble powders or dusting powders.

As an example, different compositions of soluble powders (or dusting powders) are given:

Example of PM 1:

- active substance 50%

-ethoxylated fatty alcohol (wetting agent 2.5%

-ethoxylated phenylethylphenol (dispersing agent) 5%

-chalk (inert carrier) 42.5%

Example of PM 2:

-active substance 10%

-oxo synthetic alcohol, branched

in the C13 ethoxylated form from 8 to 10

of oxides of ethylene oxide (agent for

urination) 0.75%

-neutral calcium-lignosulfonate (agent

for dispersion) 12%

-calcium carbonate (inert filler) up to 100%

Example of PM 3:

This soluble powder has the same ingredients as in the previous example, in the following proportions:

-active substance 75%

-wetting agent 1.5%

- dispersion agent 8%

-calcium carbonate (inert filler) up to 100%

Example of PM 4:

-active substance 90%

-ethoxylated fatty alcohol (diuretic agent) 4%

-ethoxylated phenylethylphenol (diapering agent) 6%

Example of PM 5:

- active substance 50%

- a mixture of surface-active agents,

anionic and nonionic (agent for

urination) 2.5%

-sodium lignosulfonate (agent for

dispersion) 5%

- kaolin clay (inert carrier) 42.5%

Aqueous dispersions and emulsions, for example compositions obtained by dissolving in water a soluble powder or a concentrate that can emulsify, and according to this invention, are included in the general scope of this invention. Emulsions can be of the water-in-oil or oil-in-water type, and can have a creamy consistency like a kind of "mayonnaise"11.

Compounds according to the invention, which can be shaped as granules that can disperse in water, also fall within the scope of the invention.

These dispersion granules, whose density is usually between 0.3 and 0.6, have a particle size which is usually between 150 and 2000, preferably between 300 and 1500 μm.

The proportion of active substance in these granules is usually between 1% and 80%, preferably between 25% and 80%.

The remaining part of the granules essentially consists of a solid filler and possibly the addition of surface-active substances that give the granules the properties needed for dispersion in water. These granules can essentially be of two types, and they differ in whether the rest of the filler is soluble in water or not. If the filler is soluble in water, it can be inorganic or, preferably, organic. Excellent results are achieved with urea.

In the case of an insoluble filler, it is recommended that it be inorganic, such as, for example, kaolin or bentonite. It is convenient that surface-active agents are added to it (in a ratio of 2 to 20% by weight of the grain), which mostly consist, for example, of at least one dispersing agent, essentially anionic, such as an alkaline or alkaline earth lignosulfonate, and the rest make diuretics, ionic or anionic, such as alkaline or alkaline earth naphthalene sulfonate.

In addition, although not mandatory, other excipients such as anti-foaming agents may be added.

The granules according to the invention are prepared by mixing the necessary ingredients and granulation according to one of the numerous known technologies (making dragees, fluidized bed, spraying, printing, etc.) usually ending with crushing with sieving to a particle size selected within the mentioned limits.

It is recommended to prepare by printing, working as indicated in the earlier examples.

Example GD 1: Granules for dispersion

90% by mass of active substances and 10% urea in granules are mixed in a mixer. The mixture is then crushed in a crushing machine. A powder is obtained which can be wetted by about 8% of mass water. The wet powder is then printed in a perforated drum printing machine. Grains are obtained which are dried, then crushed and sieved, so that grains between 150 and 2000 μm in size are provided.

Example GD 2: Granules for dispersion

The following ingredients are mixed in a blender:

-active substance 75%

-wetting agent (sodium alkylnaphthalene sulfonate) 2%

- dispersion agent (sodium polynaphthalene sulfonate) 8%

- inert filler insoluble in water (kaolin) 15%

This mixture is granulated on a fluidized bed in the presence of water, then dried, crumbled and sieved, so that granules with dimensions between 0.15 and 0.80 mm are obtained.

These granules can be used alone, in solution or dispersion with water, so that the required dose is obtained. They can also be used to prepare preparations with other active substances, especially fungicides, where the latter can be in the form of a soluble powder or granules or an aqueous suspension.

When it comes to compounds adapted for storage or transport, they contain, most advantageously, from 0.5% to 95% (by mass) of the active substance.

The invention also aims to use the compound according to the invention for combating fungal diseases of plants, for preventive effect or treatment, or for treating the soil on which they grow.

It is convenient to apply doses from 0.005 to 5 kg/ha, and especially from 0.01 to 1 kg/ha.

Claims (42)

1. Compounds containing an imidazolinone or an imidazolinthione group, indicated by the fact that they correspond to the general formula (I): [image] where: - W is a sulfur or oxygen atom or an S=O group, - A represents O or S, -n = 0 or 1, - B represents N(R5) or O or S or C(R5)(R6) or SO2 or C=O, - R1 and R2, which are identical or different, represent - H, provided that one of the 2 groups other than H or - alkyl or haloalkyl radical with 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical containing 2 to 6 carbon atoms or - dialkylaminoalkyl or cycloalkyl radical with 3 to 7 carbon atoms, or - an aryl radical containing phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted with 1 to 3 groups selected from R7 or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl have the definitions given above, or - R1 and R2 can form, with the carbon to which they are attached on the ring, a carbocycle or heterocycle having from 5 to 7 atoms, it is possible for these rings to be joined with phenyl, optionally substituted with 1 to 3 groups selected from R7; - R3 represents: - an alkyl group of 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group of 2 to 6 carbon atoms or - dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group of 3 to 6 carbon atoms, or - N,N-dialkylcarbamoylalkyl group of 4 to 8 carbon atoms or - arylalkyl group, where the alkyl part is a radical of 1 to 6 carbon atoms and the aryl part is phenyl, naphthyl, thienyl, furyl or pyridyl, optionally substituted with 1 to 3 groups selected from R7; - R4 represents: - hydrogen atom when n is equal to 1 or - an alkyl group containing 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group of 2 to 6 carbon atoms or - dialkylaminoalkyl, alkoxycarbolinylalkyl or N-alkylcarbamoylalkyl group of 3 to 6 carbon atoms or - N;N-dialkylcarbamoylalkyl group of 4 to 8 carbon atoms or - aryl radical, containing phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted with 1 to 3 groups selected from R7, or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl have the definition given above or - amino group disubstituted with 2 identical or different groups chosen from: - alkyl radicals of 1 to 6 carbon atoms, - Alkoxyalkyl, alkenyl or alkynyl radicals of 3 to 6 carbon atoms, - cycloalkyl radical of 3 to 7 carbon atoms, - arylalkyl, as defined above, phenyl or naphthyl radical, optionally substituted with 1 to 3 groups selected from R7, or - thienylmethyl or furfuryl radical - pyrrolidino, piperidino, morpholino or piperazino groups optionally substituted with an alkyl radical with 1 to 3 carbon atoms - R5 represents: - H, except when R 4 is H, or - an alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl radical containing 1 to 6 carbon atoms or - Alkoxyalkyl, Alkylthioalkyl, Acyl, Alkenyl, Alkynyl, Haloacyl, Alkoxycarbonyl, Haloalkoxycarbonyl, Alkoxyalkylsulfonyl or cyanoalkylsulfonyl radical of 2 to 6 carbon atoms, or - Alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical of 3 to 6 carbon atoms or - formyl radical or - cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical of 3 to 6 carbon atoms, or - cycloalkylcarbonyl radical of 4 to 8 carbon atoms, or - phenyl radical, arylalkylcarbonyl radical, especially phenylacetyl or phenylpropionyl radical; an arylcarbonyl radical, especially a benzoyl radical, optionally substituted with 1 to 3 groups selected from R7; thienylcarbonyl radical; furyl-carbonyl radical; pyridylcarbonyl radical; benzyloxycarbonyl radical; furfuryloxycarbonyl radical; tetrahydrofurfuryloxycarbonyl radical; thienylmethoxycarbonyl radical; pyridylmethoxycarbonyl radical; phenoxycarbonyl or phenylthiocarbonyl radical, phenyl itself being optionally substituted with 1 to 3 groups selected from R7; alkylthiocarbonyl radical; haloalkylthiocarbonyl radical; alkoxyalkylthiocarbonyl radical; cyanoalkylthiocarbonyl radical; benzylthiocarbonyl radical; furfurylthiocarbonyl radical; tetrahydrofurfuryl thiocarbonyl radical; thienylmethylthiocarbonyl radical; pyridylmethylthiocarbonyl radical; or arylsulfonyl radical, or - carbamoyl radical, optionally mono- or disubstituted with - an alkyl or haloalkyl group with 1 to 6 carbon atoms, or - a cycloalkyl, cycloalkenyl or cycloalkynyl group with 3 to 6 carbon atoms, or - an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group of 2 to 6 carbon atoms, or - phenyl, optionally substituted with 1 to 3 groups R7; - sulfamoyl group, optionally mono- or disubstituted with - an alkyl or haloalkyl group with 1 to 6 carbon atoms or - cycloalkyl, cycloalkenyl or cycloalkynyl groups with 3 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl or cyanoalkyl groups of 2 to 6 carbon atoms, or - phenyl, optionally substituted with 1 to 3 groups R7; an alkylthioalkylsulfonyl group with 3 to 8 carbon atoms or a cycloalkylsulfonyl group with 3 to 7 carbon atoms; - R6 represents: - a hydrogen atom or - cyano group, or - an alkyl group of 1 to 6 carbon atoms or a cycloalkyl group of 3 to 7 carbon atoms, or - an acyl or alkoxycarbonyl group of 2 to 6 carbon atoms, or - benzoyl group optionally substituted with 1 to 3 R7 groups; R7 presents - halogen atom or - alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical with 1 to 6 carbon atoms or - cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical with 3 to 6 carbon atoms or - nitro or cyano group, or - an amino radical, optionally mono- or disubstituted with an alkyl or acyl radical of 1 to 6 carbon atoms or an alkoxycarbonyl radical of 2 to 6 carbon atoms or - phenyl, phenoxy or pyridyloxy radical, these radicals are optionally substituted; and their salt forms, with the exception of compounds in which when R 1 and R 2 are simultaneously phenyl or simultaneously methyl, B is C(R 5 )(R 6 ), A is sulfur and W is O or S; with the exception of 3 compounds where R1=hydrogen, n=1, B=NR5, where R5 and R4=methyl, AR3=SCH3, W=O and R2 is either hydrogen, methyl or phenyl; with the exception of compounds in which R1 is phenyl, R2, R3 and R4 are methyl, n is zero and A and W are each sulfur atom; also with the exception of compounds of formula (I) in which: - n=0; and - R1 and R2 simultaneously represent methyl; and - A is a sulfur atom; and - R4 is phenyl substituted with 2 groups: - one is chosen from cyano or nitro groups or halogen atoms; the second is selected from a trifluoromethyl group or a halogen atom; and with the exception of the following compounds: - 3-[(4-chlorophenyl)sulfonyl]-3,5-dihydro-2-methoxy-5-methyl-5-(1-methylethyl)-4H-imidazol-4-one; - 2-(ethoxycarbonylmethylthio)-3-acetyl-5,5-diphenyl-3,5-dihydo-4H-imidazol-4-one; - 2-butoxy-5-ethyl-3,5-dihydro-3-methyl-5-phenyl-4H-imidazol-4-one; - 2-methoxy-5-methyl-3,5-dihydro-3(-1-phenylethyl)-4H-imidazol-4-one; - 2-methylthio-5,5-dimethyl-3,5-dihydro-3-phenyl-4H-imidazol-4-one; - 2-(methylthio)-3,5,5-triphenyl-3,5-dihydro-4H-imidazol-4-one; - 3-methyl-2-(methylthio)-1,3-diazaspiro[4.5]dec-1-en-4-one; - 3-methyl-2-(methylthio)-1,3-diazaspiro[4.5]dec-1-en-4-thione. 2. Compounds according to claim 1, characterized in that A is a sulfur atom. 3. Compounds according to claim 1, characterized in that W is an oxygen atom. 4. Compounds according to claim 2, characterized by corresponding to the general formula: [image] in which W, n and R1 to R.6 have the same meaning as in claim 1. 5. Compounds according to claim 2, characterized by corresponding to the general formula: [image] in which W and R1 to R5 have the same meaning as in claim 1. 6. Compounds according to claim 2, characterized by corresponding to the general formula: [image] in which B, n and R1 to R4 have the same meaning as in claim 1. 7. Compounds according to claim 2, characterized by corresponding to the general formula: [image] in which B, n and R1 to R4 have the same meanings as in claim 1. 8. Compounds according to any one of claims 1 to 7, characterized in that R5 is a hydrogen atom. 9. Compounds according to claim 5, characterized in that R5 is a hydrogen atom (compound Ib'). 10. Compounds according to one of claims 1 to 9, characterized in that R1 and R2 are different from a hydrogen atom. 11. The method according to one of claims 1 to 10, characterized in that R2 is an alkyl group with 1 to 3 carbon atoms. 12. Compounds according to one of claims 1 to 11, characterized in that R1 is phenyl, optionally substituted with the group R7. 13. Compounds according to one of claims 1 to 12, characterized in that R3 is an alkyl group with 1 to 3 carbon atoms. 14. Compounds according to one of claims 1 to 13, characterized in that R4 is phenyl, optionally substituted with the group R7. 15. Compounds according to one of claims 1 to 14, characterized in that R3 is a methyl radical. 16. Method for preparing (method A) compounds of formula (I) according to claim 2, characterized in that the solvents 2-thiohydantoins of formula (II) are S-alkylated with a compound of formula R3X, in the presence of a base and a solvent, according to the scheme: [image] in which R1, R2, R3, R4 and W have the meanings of claim 1 and X is a chlorine, bromine or iodine atom or a sulfate group or an alkylsulfonyloxy or arylsulfonyloxy group. 17. Process for obtaining 2-methylthio-2-imidazolin-5-one compound of formula (Ic) (process B) according to claim 6, characterized in that the compound of formula (V) is cyclized by simple heating in an aromatic solvent at reflux, according to the scheme : [image] in which R1, R2, R4, B and n have the same meanings as in claim 1. 18. Process for obtaining the compound of formula (V) (process B) according to claim 17, characterized in that the iminodithiocarbonate of formula (III) is condensed with hydrazine of formula (IV) according to the scheme: [image] where: - R1, R2 and R4 have the same meaning as in claim 1, - n is equal to 1 and B represents NR5, - R5 has the same meaning as in claim 1; wherein the acid (III) should be activated for this condensation in the form of acid chloride, dicyclohexylated using dicyclohexylcarbodiimide or in the form of imidazole, using carbonyldiimidazole. 19. Procedure for obtaining the compound according to formula (lb) (procedure C1), according to the scheme: [image] characterized by the fact that the compound of the formula R5X reacts in a solvent in the presence of a base, with the compound of the formula (Ib) according to claim 5, in which the R5 group is a hydrogen atom according to claim 9 (compound (Ib')), the R1 to R4 groups have the meaning given in according to claim 1, the group R5 is an alkyl, alkoxycarbonyl, acyl, aroyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl group and X represents a leaving group, such as halogen, sulfate group, optionally substituted phenoxy, R5O when R5 is acyl, or alkylsulfonyloxy or arylsulfonyloxy group or a non-leaving group such as isocyanate or isothiocyanate. 20. Procedure for obtaining the compound of formula (Id) (procedure C2), according to the scheme: [image] indicated by the fact that the compound of the formula (Id) according to claim 7, in which R2 is a hydrogen atom (compound Id')), reacts with the compound of the formula R2X in a solvent and in the presence of a base, at a temperature between -30° and +80°C, X is a chlorine, bromine or iodine atom and R1 to R4, B and n have the same meaning as in claim 1. 21. The method according to claim 20, characterized in that the base is selected from the group consisting of alkoxide, metal hydride and amide and the solvent is selected from the group consisting of ethers, cycloethers, dimethylformamide, dimethyl sulfoxide and aromatic solvents. 22. Process for obtaining the compound of formula (I) (process D) according to claim 1, in which the compounds W represent the S=O group, characterized in that the S-oxidation of the compound of formula (I) in which W is a sulfur atom is carried out, at whereupon the oxidation of 2-imidazolin-5-thione was carried out with a stoichiometric amount of peroxide in the solvent at a temperature between -20°C and +20°C. 23. The method for obtaining according to claim 22, characterized in that the peroxide is a peracid and the solvent is selected from the group consisting of chloroform and methylene chloride. 24. Compounds that are used in particular as intermediates in the preparation of the compound according to one of claims 1 to 15, indicated by the fact that they correspond to formulas Ha, III, V and VIla: [image] wherein W, R1, R2, R4, R5, n and B are as defined in claim 1, R4 is other than a hydrogen atom, with the exception of compounds of formula IIa with: W=S R1=methyl, R2=:phenyl, R3=hydrogen and R4=methyl or phenyl; W=S, R1=ethyl, R2:=phenyl, R4=methyl and R5=hydrogen; W=S, R1=methyl, R2=p-tolyl, and R4 = methyl, R5 = hydrogen or methyl, or R4=phenyl, R5=hydrogen; W=S, R1 and R2 = phenyl R4 = methyl and R5 = H, and with the exception of the compound according to formula VIIa with: R4=methyl, R5=methyl, R1= hydrogen and R2=methyl or phenyl. 25. Compounds according to claim 24, characterized in that R5 is a hydrogen atom, R2 represents an alkyl group with 1 to 3 carbon atoms, R1 represents a phenyl ring, optionally substituted with R7, R4 represents a phenyl ring, optionally substituted with R7, and R7 is defined as in claim 1. 26. Compounds according to claim 24 or 25, characterized in that they correspond to formula VIIa. 27. Compounds according to claim 25 or 26, characterized in that R2 represents a methyl group. 28. Compounds according to claim 25, 26 or 27, characterized in that R1 represents a phenyl nucleus. 29. Process for obtaining 2-thiohydantoin of formula (VII) (process F): [image] characterized by the fact that before cyclization, the compound of formula (IV) R4(B)nNH2 reacts with isothiocyanates derived from amino acids of formula (VIII): [image] in which the hydantoins R1, R2 and R4 have the same meaning as in claim 1, n=1 and B represents N(R5). 30. The method according to claim 29, characterized in that the cyclization is performed thermally, by heating the reactant mixture at a temperature between 110 and 180°C in an aromatic solvent, such as toluene, xylene or chlorobenzenes. 31. The method according to claim 29, characterized in that the cyclization is performed with one equivalent of the base in the solvent and at a temperature between -10 and 80°C, the mixture is then neutralized at ambient temperature. 32. The method according to claim 31, characterized in that the base is selected from the group consisting of an alkaline alkoxide, an alkaline hydroxide or a tertiary amine; the solvent is selected from the group consisting of ethers, cyclic ethers, alcohols, esters, DMF and DMSO. 33. Process (process G) according to claims 29 and 31, characterized in that, before obtaining the 2-thiohydantoin derivative by neutralization in an acidic medium, the use of alkyl halide R3X in order to form the compound of formula Id, X is a chlorine, bromine or iodine atom or alkylsulfonyloxy or arylsulfonyloxy group and R3 has the same meaning as in claim 1. 34. A fungicidal composition that contains, a combination of one or more solid or liquid carriers that are acceptable in agriculture and/or a surfactant that is also acceptable in agriculture, one (or more) active substances selected from compounds of formula I as defined in one from requirements 1 to 15. 35. Fungicidal composition according to claim 34, characterized in that it contains 0.5% to 95% by weight of compounds according to one of claims 1 to 15. 36. Fungicidal composition according to claims 34 or 35, characterized in that it contains a combination of the compound of formula I with another active material. 37. Composition according to claim 36, characterized in that the second active material is a fungicide. 38. Compositions according to claim 36 or 37, characterized in that they can be obtained from granules containing the compound of formula I and form wettable powders or aqueous suspensions containing another active substance. 39. Compositions according to claim 38, characterized in that the second active substance is a fungicide. 40. A method for treating crops that are attacked, or may be attacked by fungal diseases, characterized in that an effective amount of the active compound according to one of claims 1 to 15 or the composition according to claims 34 to 39 is applied preventively or curatively. 41. The method for treating crops according to claim 40, characterized in that the effective dose is between 0.005 and 5 kg/ha. 42. The method for treating crops according to claim 41, characterized in that the effective dose is between 0.01 to 1 kg/ha.