SI9200391A - Fungicidal 2-imidazolin-5-one and 2-imidazolin-5-thione derivatives - Google Patents

Abstract

The invention relates to 2-imidazolin-5-one or 2-imidazoline-5-thione derivatives of general formula (I) <IMAGE> in which, - W is a sulphur or oxygen atom or the S=O group, - A represents O or S - n = 0 or 1 - B represents NR5 or O or S or CR5R6 or SO2 or C=O - R1 to R4 represent a hydrogen atom or a hydrocarbon radical, optionally substituted, especially by halogen atoms. The invention also relates to the preparation of these compounds and to their use as broad-spectrum fungicides.

Description

Agrochimie

FUNGICIDES DERIVATIVES 2-IMIDAZOLIN-5 ONES

AND 2-IMIDAZOLINE-5-TIONES

FUNGICIDES DERIVATIVES 2-IMIDAZOLIN-5-ONES

AND 2-IMIDAZOLINE-5 -TIONS

The present invention relates to novel compounds of imidazolinone or imidazoline thionine used in the treatment of plants. The same applies to the processes for the preparation of the aforementioned compounds and products possibly usable as intermediates in the preparation processes. It further relates to the use of these compounds as fungicides, to fungicidal compositions based on these compounds, and to combat the fungal diseases of the cultures in which we use these compounds.

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

Another object of the present invention is to provide compounds that represent an equally improved spectrum of use in the field of fungal diseases.

We have now discovered that these objectives can be achieved by the products of the invention which are derivatives of 2-imidazolin-5-ones or 2-imidazolin-5-thione of general formula (I)

(B) n - R ₄

W

A-R ₃ (I) where:

- W is a sulfur or oxygen atom or an S = O group.

- A is O or S

- n = 0 or 1

- B is N (R 4) or O or S or C (R ₅ ) (R 8) or SO ₂ or C = O.

- R- ^ and R ₂ , identical or different, are:

- H, provided that one of the two groups is other than H, or

an alkyl or haloalkyl radical having 1 to 6 carbon atoms or

- alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radicals having 2 to 6 carbon atoms, or

a dialkylaminoalkyl or cycloalkyl radical of 3 to 7 carbon atoms, or

- an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl optionally substituted by 1 to 3 groups selected from R ₇ or

- arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl being defined above, or

R ₂ and R ₂ may form, to the ring-linked carbon, a carbocycle or heterocycle having 5 to 7 atoms, these rings may be combined with phenyl optionally substituted by 1 to 3 groups selected from R ₇ ;

- R ₃ ^ θ:

an alkyl group of 1 to 6 carbon atoms or

- alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or

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

- N, N-dialkylcarbamoylalkyl group having 4 to 8 atoms or

- an arylalkyl group, the alkyl moiety being a radical of up to 6 carbon atoms, the aryl moiety being phenyl, thienyl, furyl, pyridyl optionally substituted by 1 to 3 groups selected from R ₇ ;

-R ₄ is:

a hydrogen atom when n is 1 or

an alkyl group of 1 to 6 carbon atoms or

- alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or

- a dialkylaminoalkyl, alkoxycarbonyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or

- N, N-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms or

- an aryl radical comprising phenyl, naphthyl, thienyl, furyl pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl optionally substituted by 1 to 3 groups selected from R ₇ or

- arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl being as defined above, or

- an amino group disubstituted with 2 identical or different groups selected from:

- an alkyl radical of 1 to 6 carbon atoms,

- alkoxyalkyl, alkenyl or alkynyl radicals having 3 to 6 carbon atoms,

- cycloalkyl radical of 3 to 7 carbon atoms,

- an arylalkyl radical such as defined above, phenyl or naphthyl optionally substituted by 1 to 3 groups selected from R _7, or

- thienylmethyl or furfuryl radical,

- a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted by alkyl having 1 to 3 carbon atoms;

- ^R s 3θ ^:

- H, unless R _{4 is} H, or

- alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl having 1 to 6 carbon atoms, or

- alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, or quinyl, haloalkyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl, cyanoalkylsulfonyl having 2 to 6 carbon atoms, or

- alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl radical of 3 to 6 carbon atoms, or

- formyl radical, or

- cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl, alkynylcarbonyl radical of 3 to 6 carbon atoms, or

- a cycloalkylcarbonyl radical having 4 to 8 carbon atoms, or

- phenyl radical; arylalkylcarbonyl, in particular phenylacetyl and phenyl propionyl; arylcarbonyl, in particular benzoyl, optionally substituted with 1 to 3 groups selected from R _7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or phenylthiolcarbonyl, the phenyl itself being optionally substituted with 1 to 3 groups selected from R ₇ ; alkylthiolcarbonyl; haloalkylthiocarbonyl; alkoxyalkylthiolcar bonyl; cyanoalkylthiocarbonyl; benzylthiocarbonyl; furfurylthiocarbonyl; tetrahydrofurfurylthiolcarbonyl; thienylmethylthiol carbonyl; pyridylmethylthiolcarbonyl; or arylsulfonyl or

- carbamoyl radical, possibly mono or substituted with

an alkyl or haloalkyl group having 1 to 6 carbon atoms or

a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or

an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or

- phenyl optionally substituted by 1 to 3 groups R ₇ ;

- sulfamoyl group, possibly mono or disubstituted by

an alkyl or haloalkyl group having 1 to 6 carbon atoms or

a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or

an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or

- phenyl optionally substituted by 1 to 3 groups R ₇ ;

- an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or a cycloalkylsulfonyl group of 3 to 7 carbon atoms;

- * ₆ Πθ ^:

- a hydrogen atom or

- cyano group or

an alkyl group of 1 to 6 carbon atoms or cycloalkyl of 3 to 7 carbon atoms, or

an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms, or

- a benzoyl group optionally substituted by 1 to 3 R ₇ groups;

-R _? is:

- a halogen atom or

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

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

- a nitro or cyano group, or

- an amino radical optionally mono or substituted with an alkyl or acyl radical of 1 to 6 carbon atoms or alkoxycarbonyl of 2 to 6 carbon atoms, or

- a phenyl, phenoxy or pyridyloxy radical, these radicals being optionally substituted;

and salts thereof.

Certain particular compounds of the formula I whose formula is 1a are known.

where w, to R ₆ and n have the same meaning as in formula I.

Labeled as S-alkyl derivatives of 5,5-diphenyl-2-thiohydantoin and

In particular, 5,5-diphenyl dithiohydantoins have been studied for their pharmacological properties:

a) Zejc, A .; Dissertationes Pharmaceuticae et pharmacologicae. Warschau, 20 (5), 507-524 and 525-537 (1968)

b) Luka-Sobstel, B.; Zejc, A.; Dissertationes 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)

They did not describe any fungicidal agricultural activity of these compounds and.

Boehme, Martin et Fears are in Archiv der Pharmazie 313,

10-15 (1980) (ref. D) described other individual compounds of formula I. These are the 3 following compounds:

R = H, CH3, Phenyl.

These compounds are therefore included in the compounds of formula Ib which are part of the invention:

where W and 1 ^ to R _{5 have the} same meaning as in formula I.

The compounds of formula I can be prepared by known methods described in the references previously provided and in the following references:

e) Biltz, 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) 354-365

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.; Tarnas, J.; Tetrahedron 29 22, 3571-3578 (1973)

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

l) Muraoka, M.; Journal of the Chemical Society Perkin Transaction I, (1990), 3003-3007, or following the procedures A, B, C, or D described below.

PROCEDURE A: A process for the preparation of compounds of formula (I). The preparation of compounds of formula (I) by S-alkylation of 2-thiohydantoins (II) is carried out according to the reaction scheme:

Base + r ₃ x -► (D

The solvent is bromine or iodine, or sulphate attempts (Π) in which X is a chlorine atom, pins, or an alkylsulfonyloxy or arylsulfonyloxy group, with the alkyl and aryl are as defined above for R and R _2nd Alcohol, for example, potassium tert-thiobutylate, alkali metal or alkaline earth metal hydroxide, alkali metal carbonate or tertiary amine may be used as the base.

Ethers, cyclic ethers, alkyl esters, acetonitrile, alcohols with 1 to 3 carbon atoms, aromatic solvents, for example tetrahydrofuran, at a temperature in the range of -5 ° C to + 80 ° C can be used.

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

The 2-thiohydantoins of formula (II) can be obtained by the procedures described in the literature, such as in the following references:

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

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

o) Carrington C. H.; Journal of the Chemical Society (1947)

681-686

g) Carrington C. H.; Viarring, W. S.; Journal of the Chemical Society (1950) 354-365

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

i) Koltai, E.; Nyitrai, J.; Lempert, K.; Burcis, L.; Chemische Berichte 104, 290-300 (1971), or by one of the processes E or F described below, which are part of the invention.

PROCEDURE B: Preparation of Compounds Ic.

The preparation of 2-methylthio-2-imidazolin-5-ones of formula (Ic) by cyclization of iminodithiocarbonates of formula (V) is carried out according to the global scheme:

R, NH ₂ ^a > X + cs ₂ + ₂ ch ₃ and Rf CO ₂ H

Base

b)

N = C sch ₃ 'SCH,

R ₄ - (B) n-NH ₂ (IV)

Rf CO ₂ H (UD

R ₂ .

R

Λ / r— ^ sch ₃

N = Cf ³

SCH ₃

C — NH— (B) n — R ₄ (V) _X SCH ₃ 'SCH ₃ ^c ) r /' c — NH— (B) n — R ₄ O (V)

(Ic)

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

- C. Alvarez Ibarra et al .; Tetrahedron Letters, 26 (2), 243-246 (1985)

- E. Melendez et al .; Synthesis 1981, 961 by:

R ₂ nh ₂

Rf CO ₂ H + CS ₂ + 2 CH 3 I

Base

-► (IH)

b) Compounds of formula (V) are obtained by condensation of compounds of formula (III) with amines or hydrazines of formula (IV). In order to obtain condensation, acid (III) in the form of acid chloride, dicyclohexylisourea with dicyclo12 hexylcarbodiimide or imidazole with carbonyldiimidazole was required. Condensation was performed under the conditions usual for this type of reaction e.

c) The cyclization of compounds (V) was realized by simple heating in an aromatic solvent at reflux. In particular, xylene, chlorobenzene or dichlorobenzene may be used as the solvent.

PROCEDURE C: .Derivatizing compounds (Ib ') and (Id').

PROCEDURE Cl: Preparation of Compounds Ib by N Derivatization of Compound Ib '.

Compounds of formula (Ib ') (compounds (Ib) in which R1 is a hydrogen atom) can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulfamoylated according to the following general scheme:

Here, R _{5 is an} alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl group, such as defined above.

X is a halogen, a sulfate group or a phenoxy optionally substituted, or an alkylsulfonyloxy or arylsulfonyloxy group, or a R ₅ O group when R _{5 is} acyl.

Alkali metal hydrides, alcohols or a tertiary amine may be used as the base. The reaction can be performed at a temperature in the range of -30 ° C to + 50 ° C. For example, ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents may be used as solvent.

Carbamoylation of compounds (Ib ') can be accomplished by reaction with isocyanates or isothiocyanates according to the scheme:

The reaction is carried out in the same manner described above, but in the exact amount.

conditions such as those which can be used in the catalyst PROCEDURE C2: Preparation of Compounds Id

Compounds Id '(compounds Id in which R _{2 is} a hydrogen atom) can be alkylated at position 4 according to the scheme:

X is a chlorine, bromine or iodine atom. An alcoholate, metal hydride or amine salt may be used as the base. The reaction can be carried out at a temperature between -30 ° C and + 80 ° C. Ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents may be used as solvents.

PROCEDURE D: Preparation of 2-imidazoline-5-thione S-oxide derivatives.

The compounds of formula (I) in which W is the group S = 0 were obtained by oxidation of 2-imidazoline-5-thione according to the scheme:

Peroxides can be used as the oxidant, especially peracids The oxidant must be used in stoichiometric quantities. The oxidation is carried out in chloroform or in methylene chloride at a temperature in the range of -20 ° C to + 20 ° C.

PROCEDURE E: Preparation of dithiohydantoins of formula (IV).

Dithiohydantoins of formula (VI) can be obtained by binding anions in the alpha position of isothiocyanates with non-anion-free isothiocyanates according to the scheme:

R _{x -} CH - N = C = S +

At least one of the R ₂ or R ₂ groups must attract electrons (aryl, substituted aryl, alkoxycarbonyl ...). The isothiocyanate R ₄ -NCS may not be capable of becoming an anion; arylisothiocyanates are particularly useful in this reaction.

Potassium tert-thiobutylate may be used as the base. lithium bis (trimethylsilyl) amine and alkali metal hydrides. Ethers, cyclic ethers can be used as solvent. The reaction is carried out at a temperature lower than -60 ° C. The anion must bind at the same moment it forms. Therefore, pour a mixture of 2 isothiocytes onto a solution of the base at a temperature lower than -60 ° C.

PROCEDURE F: Preparation of 2-thiohydantoins of formula (VII). 2-Thiohydantoins (VII) are prepared starting from isothiocyanates, which are derivatives of amino acids (VIII) after the reaction:

R ₁ -CN = C = S + CO, R

R ₄ - (B) n-NH ₂

There are two ways to achieve cyclization:

- thermal: in this case, heat the mixture of reagents at a temperature in the range of 110 ° C to 18O ° C in an aromatic solvent such as toluene, xylene, chlorobenzenes.

- in the base environment: is carried out in the presence of an equivalent of a base such as an alkali metal alcoholate, an alkali metal hydroxide or a tertiary amine. Under these conditions cyclization occurs at a temperature between -10 and + 80 ° C. As a solvent, ethers, cyclic ethers, alcohols, esters, DMFs, DMSOs can be used ....

PROCEDURE G: Preparation of compounds of formula I in one phase.

If cyclization of 2-thiohydantoins by process F is carried out in a basic medium, then at the end of the reaction, the thiohydantoin will be present in the form of a thiolate, which can react directly with an alkyl halide or sulfate of R ₃ X or with R ₃ X in which X is alkylsulfonyloxy or arylsulfonyloxy to form (I). In this way, we connect the procedures A and F according to the scheme:

R, —C — N = C = S + ¹ I

CO ₂ R

B'M ⁺

R ₄ - (B) n-NH ₂ -►

PROCEDURE H: Preparation of compounds of formula only.

in which (B) n is a sulfur atom.

These compounds can be obtained by reacting the sulfide chloride R ^ SCl with imidazolinone of formula IX according to the scheme:

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

Preferred compounds for their best fungicidal activity and / or ease of synthesis are:

1) compounds of formula Ib,

2) compounds of formula I, in particular Ib, in which Rc is a hydrogen atom,

3) compounds wherein R

4) compounds in which R _{2 is} carbon,

5) compounds in which R _{x is} substituted by R ₇ ,

6) compounds in which R _{3 is} carbon,

7) compounds in which R _{4 is} substituted with R ₇ ,

8) compounds in which R ₃ and R _{2 are} other than H, an alkyl group of 1 to 3 atoms phenyl core, optionally a subalkyl group of 1 to 3 atoms phenyl core, optionally a submethyl group.

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

The structures of all products were determined by at least one of the following spectral techniques: proton NMR spectrometry o, η ...

C NMR spectrometers, infrared spectrometers m mass spectrometry.

In the tables given below, the methyl or phenyl radicals were designated Me and Ph, respectively. however, it represents a physical constant, that is, either a melting point (T1) or a refractive index (nD ²⁰ ).

EXAMPLE 1_L Preparation of Compound M PQ Procedure ZL ·.

Dissolve 0.9 g (3 mmol) of 3-benzyl-5-methyl-5-phenyl-2-thiohydantoin in 30 ml of anhydrous tetrahydrofuran. This was cooled to 0 ° C and then 0.34 g (3 mmol) of potassium tert-thiobutylate was added. Let it react for 10 min. at 0 ° C and then poured dropwise at this temperature of 0.46 g (3.3 mmol) of methyl iodide: a precipitate of potassium iodide was observed. Let the temperature rise to room temperature. The reaction mixture was diluted with 100 ml of ethyl acetate. Wash the solution twice with 100 ml of water each. The solution was dried over sodium sulfate and then treated with activated charcoal. The solution was concentrated under reduced pressure: 0.6 g of 1-benzyl-4-methyl-2-methylthio-4-phenyl-2-imidazolin-5-one (compound 34) was obtained as a solid yellow solid. melts at 68 ° C.

In the same manner, the compounds described below were prepared:

St. R2 R3 R4 R5 W Const. 1 Me Me Ph H S Ti = 127 ° c 3 Me 2 -oxoproF il Ph H s Tr = i3o ° c 9 Me Me Ph H 0 Tf = 149 ° c 10 Me Me me t β- ίοΙ il H 0 TI = 124 ° C 11 Me Me ^p ara — tolί ¹ H 0 TI = 150 ° C 12 Me Et Ph H 0 118 = 118 ° C 13 Me Me ⁴ —F 1 hour of ^h H 0 Tf = 144 ° C 14 Me Alil Ph H 0 TI = 92 ° C 15 Me Me ° rto — toli 1 H 0 Tf = 92 ° C 16 Me Me 3 — chloroPt ¹ H 0 ΤΓ = 120 ° C 17 Me 1 isopropyl Ph H 0 Tf = 95 ° C 18 Me . 1 Me 4-chloroPf 2 H 0 TI = 149 ° C 19 Me terti boots 1jj 0 Tf = 73 ° C 20 Me Me > -k 1 or oPh H 0 Tf = 134 ° C 21 Me Me - (CHa) e- 0 nD ²⁰ = 1.551 22 Me Me Ph Me 0 Tf = 124 ° C 23 Me Me Ph Aceti1 0 Tf = 132 ° C 24 Me Me ⁴ —Methoxy I Ph h 0 Tf = 138 ° C 25 Me n-propi1 Ph I H 0 Tf = 90 ° C 40 Me Me 2 1 -methoxy » _{H H} 0 Tf = 1io ^e c 41 Me Me Aceti1 H 0 Tf r55 ° C

43 Me - Me 4-NOz-Ph H 0 ti = 133 ° C 44 Me - Me [ 2-Pyridyl H S Mp = 114 ° C 45 Me Me 1 2-Pyridyl H 0 TI = 147 ° C 46 Me 1 1 Me 3-pyridyl H 0 TI = 14O ° C 47 Me 1 I Me 3-pyridyl H S TI = 176 ° C 54 Me -] MeS ⁵ i16 «Me» Ph H S TI = 146 ^e C 73 Me MeS 2-thia zolil Me 0 TI = 116 ° C 75 Me CHF _a S Ph H 0 Mp = 80 ° C 80 Me MeS: 5-pyrides CH = L 0 Mp = 92 ° C 81 Me MeS _: 2-Pyrides CH = L 0 Ti = 106 ° C 82 Me MeS 4-Me SO2-Ph H 0 Mp = 130 ° C

St. R2 R3 R4 n R5 w Const. 26 Me Me Ph 0 - s TI = 123 ° C 27 Ph Me Ph 0 - s Π = 120 ° C 28 Me Me Me 0 - s Mp = 85 ° C 29 Ph Me Me 0 - s π = 144 ° C

St. R2 R3 R4 n R5 W The benefit. 30 Me Me Ph 0 0 Mp ₇₀ ° _C 31 Me Me Me 0 0 ^Tf = 58 ° C 32 Ph Me Me 0 - 0 ^Tr = 170 ° C 33 H Me Ph 0 - 0 ^T »= 250 ^e C 34 Me Me Ph 1 H 0 Ti = 68 ° C 35 Me Me 2-tieni L 1 H 0 ^TF = 76 ° C 36 Me Me Me 1 Me 0 nD20 = U53 37 Me Me 2- f ur 1 ..... H 0 med 38 Me Me 2 ►-pyrides 1 0 0 med 50 Ph MeS Me 0 H s Tf _{= 144} o _C 52 Me MeS Ph 1 (CH) E ? 0 med 57 Me MeS 2-MePh 0 - 0 med

We prepared the same:

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

- 4-Phenyl-4-methyl-1- (benzyloxy) -2-methylthio-2-imidazolin5-one (Compound 56: honey).

EXAMPLE 2-L Preparation of Compound 1 Procedure IL_

a) N- [bis (methylthio) methylene J-2-phenyl glycine (compound III) with R ₁ = phenyl and R ₂ = H) ^:

At + 5 ° C, dissolve 100 g (0.66 mol) of phenylglycine in 335 g of a 22% (1.3 mol) aqueous potassium hydroxide solution. Add 55.3 g of carbon sulfide while vigorously stirring the reaction mixture: a precipitate appears and the mixture is colored orange. Allow to react for 3 hours at room temperature, then pour 22 ml of 103 g (0.73 mol) of methyl iodide, while maintaining this. perature of the reaction mixture below 3 0θ <3. Leave to react for half an hour and then add 74 g (0.66 mol) of 50% potassium hydroxide solution. Leave to react for half an hour and then pour again 103 g of methyl iodide and leave to react for 1 hour. The mixture is diluted with 300 ml of water. With IM hydrochloric acid, acidify to pH = 4. The product was extracted with 500 ml of ethyl acetate. The solution was dried over magnesium sulfate and then concentrated under reduced pressure. 49.5 g of N- [bis (methylthio) methylene-2-phenylglycine (31% yield) are obtained as a yellow solid which melts at 112 ° C.

b) [n- (bis (methylthio) methylene) -2-phenyl glycylmethane-chlorophenyl hydrazide (compound V with R ₁ = phenyl, R2 = H, R4 ⁼ mta-chlorophenyl, n = 1, B = NH):

To a solution of 2.95 g (16.4 mmol) of N- [bis (methylthio) methylene-2 phenyl glycine in methylene chloride (40 ml) was added 3.38 g (16.4 mmol) of dicyclohexylcarbodiimide and then allowed to react for half an hour at room temperature. temperature. 2.34 g (16.4 mmol) of meta-chlorophenylhydrazine are added. Heat at 30 ° C for half an hour. The insoluble matter is filtered. The filtrate is washed twice with 30 ml of water each. The solution was concentrated: honey was obtained, which was purified by chromatography on a silica column. After purification, 2.5 g of [n- (bis (methylthio) methylene) -2-phenyl glycyl) meta-chlorophenyl hydrazide are obtained in the form of a pink powder, which melts at 146 ° C.

c) 1-Metachlorophenyl-2-methylthio-4-phenyl-2-imidazolin-5-one (Compound No. 7)

Dissolve 1.92 g (5 mmol) of fN- (bis (methylthio) methylene) -2-phenyl glycyl] meta-chlorophenyl hydrazide in 30 ml of xylene. The reaction mixture was heated at reflux for 4 hours. Concentrate the mixture under reduced pressure. The resulting honey is stirred with 10 ml of ether: the product crystallizes. The precipitate was filtered and the product was dried in a desiccator under vacuum. Thus, in a yield of 56%, compound no. 7 as a yellow powder, melting at 196 ° C.

Acting in a similar way, we prepared the compounds presented in the following table:

St. R2 R3 R4 R5 W Kanst. 4 H Me 2-chloroF h H 0 ^{T {} = 130 ° C 5 H Me | Ph H 0 ^Ti = 190 ° C 6 H Me 4-chloroPI and H 0 ^Ti = 162 ° C 7 H '1 i Me 3 — k1oroPh H 0 ^Mp = 196 ° C 8 H - -, - j- Me meta-toli1 H 0 ^Ti = 182 ° C 59 H -, - _f - MeS 2,4- <CHs) _with Ph H 0 Ti = 64 ° C 61 H -, -, - MeS 2 »5— (CHs) aPh H 0 T · = 162 ° C 63 H MeS I 2-EtPh H 0 T »= 1266C 69 H MeS 2.5— (Cl) zPh H 0 Ti = 144 ° C 71 H -, -, - MeS 3.5— (Cl) aPh H 0 Tf = 146 ° C

4-Phenyl-1- (N-phenylamino) -2-methylthio-224 imidazolin-5-one (compound 120) was prepared equally.

EXAMPLE Preparation of 4-methyl-1- (N-methyl-N-phenylamino) -2-methylthio-4-phenyl-2-imidazolin-5-one (Compound # 221 2 by alkylation (methylation) by the method of CI,

To 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) previously cooled to 0 ° C, 0.4 g (3.5 mmol) of potassium tert-thiobutylate were added. Let it react for half an hour at 0 ° C. Then 0.5 g (3.5 mmol) of methyl iodide was added and then allowed to react for half an hour at room temperature. The reaction mixture was poured into 100 ml of water and the product extracted with 100 ml of diethyl ether. The ether solution was dried over magnesium sulfate and then concentrated. The product was crystallized by trituration into 10 ml of diisopropyl ether. It is filtered and then dried under vacuum. 0.73 g (yield: 70%) of compound 22 are thus obtained in the form of a light yellow powder, which melts at 124 ° C.

EXAMPLE Preparation of 4-methyl-1- (N-acetyl-N-phenylamino) -2-methylthio-4-phenyl-2-imidazolin-5-one (Compound 221 by aoylating ero. £ 1 ^

To a solution of 4-methyl-1-phenylamino-2-methylthio-4-phenyl-2-imidazolin-5-one (compound 9) (1 g; 3.2 mmol) in anhydrous tetrahydrofuran (30 ml) previously cooled to 0 ° C, 0.4 g (3.5 mmol) of potassium tert-thiobutylate were added.

Let it react for half an hour at 0 ° C. Then 0.25 g (3.5 mmol) of acetyl chloride was added and then allowed to react for half an hour at room temperature. The reaction mixture was poured into 100 ml of water and the product extracted with 100 ml of diethyl ether. Wash the ether solution with water until neutral. This is dried over magnesium sulphate and then concentrated. This produces honey, which is purified by chromatography on a silica column. The purified product crystallizes in diisopropyl ether. 0.25 g of compound no. 23 in the form of a white powder, melting at 132 ° C.

In a similar manner, compounds No. 39 and 42.

St. R2 R3 R4 R5 W Const. 23 Me Me Ph Aceti1 0 Tf = 132 ° C 39 Me Me Ph Forms 1 0 med 42 Me Me Ph tBuOCO 0 med

EXAMPLE 5 Preparation of 4-ethyl-2-methylthio-4-phenyl-1-phenylamino 2-imidazolin-5-one (LSI compound by process 022

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 was added 0.55 g of potassium tert-thiobutylate. Allow to react for 30 minutes at room temperature and then add

0.8 g (5.05 mmol) of ethyl iodide. Leave to react for 1 hour at room temperature. The reaction mixture was diluted with 150 ml of ethyl acetate. The solution is washed with water and then concentrated under reduced pressure. The product was purified by column chromatography on silica (Merck silica 6OH; eluant: 25% ethyl acetate / 75% heptane). 0.65 g of compound no. 48 in the form of a very light brown powder, which melts at 147 ° C.

In the same manner, compound no. 49.

St. R2 R3 R4 R5 W The benefit. 48 Et Me Ph H Oh π = 147 ° C 49 i so — prop 1 Me Ph H 0 Ti = 135 ° C 60 Me MeS 2 , 4- (Me> 3El Ph H 0 med 62 Me - _r , - MeS 2,5- (Me) «Ph h 0 Mp 160 ° C 64 Me MeS 2-EtPh H 0 med 65 Me MeS 2 , 4- (CD, Ph H 0 66 Me 1 * MeS l-naphthyl H 0 ^Tr - 174 ° C 70 Me MeS 2.5 (01) ^ H 0 ^Tf xl80 ° C 72 Me * 1 MeS 3,5- (Cl) aPh H 0 ^Mp -200 ° C 74 CHF2 MeS Ph H 0 ^Mp 124 ° C 79 Me MeS 2-CF ₃ Ph H 0 ^Ti c91 ° C

4-Methyl-2-methylthio-4- (4-fluorophenyl) 1-phenylamino 2-imidazolin-5-one (Compound 68) was prepared equally.

EXAMPLE 6_l Preparation of Compound 2. PP Procedure IL.

Dissolve 1.7 g (5.2 mmol) of 4-methyl-2-methylthio-4-phenyl-phenylamino-2-imidazoline-5-thione (compound No. 1) in 20 ml of chloroform. The solution was cooled to -10 ° C and then a solution of 1.35 g (5.5 mmol) of meta-chloroperbenzoic acid and 30 ml of chloroform was added over 10 minutes. After the addition is complete, allow the temperature to rise to room temperature. The reaction mixture was washed with saturated aqueous sodium bicarbonate solution and then with distilled water. The organic phase is treated with activated charcoal and then concentrated. The honey obtained is collected with 20 ml of ether: it dissolves and then a very light brown solid precipitate appears. The precipitate was filtered. The product is dried under reduced pressure. Thus 0.4 g (yield: 25%) of compound no. 2 in the form of a very light brown powder, which melts at 150 ° C.

St. R2 R3 R4 R5 W Conv. 2 Me Me Ph H s = o Mp -150 ° C

EXAMPLE 2 Pipylate 3.5-Diphenyl-5-methyl-2-thiohydantoin pp. Procedure E

Dissolve 4.7 g (20 mmol) of 2-isothiocyanato-2-phenyl ethyl propionate in 40 ml of xylene. 2.16 g (20 mmol) of phenylhydrazine are added and then refluxed for 4 hours. Cool to room temperature, a solid very light brown precipitate appears. The precipitate was filtered; it was washed with 5 ml of diisopropyl ether and then dried in vacuo. 4.6 g (yield: 77%) of 3,5-diphenyl-5-methyl-2-thiohydantoin are thus obtained in the form of a very light brown powder, which melts at 164 ° C.

EEIMEfi 2_l Eiiprava 5-methyl-5-phenyl-3- (2-pyridylamino) -2-thiohydantoin according to procedure F

Dissolve 2 g (9 mmol) of methyl 2-isothiocyanato-2-phenyl propionate in 30 ml of tetrahydrofuran. A solution of 0.99 g of 2-hydrazinopyridine and 10 ml of tetrahydrofuran is added: the temperature of the reaction mixture is raised from 20 to 30 ° C and a solid precipitate appears. Let it react for half an hour at 30 ° C, then cool to 5 ° C. Then a solution of 1 g of potassium tertiobutylate and 10 ml of tetrahydrofuran is added: the mixture turns purple. Allow the temperature to rise to room temperature and allow to react for 2 hours. Pour the mixture into 150 ml of water. With acetic acid, the mixture was neutralized. The product was extracted with 150 ml of ethyl acetate. The solution was washed with water, dried over magnesium sulfate and treated with activated charcoal. The product was then concentrated and allowed to crystallize into 20 ml of diethyl ether. The precipitate was filtered and then dried in vacuo. 1.6 g (yield: 60%) of 5-methyl-5-phenyl-3- (2-pyridylamino) 2-thiohydantoin are obtained, a light yellow solid which melts at 80 ° C.

According to this process, compounds of formula (VII), intermediates of compounds of formula I, and those numbered starting with no. 1001 and which are grouped in the following table:

(VH)

R1 = methyl R2 = -phenyl

St. n B R4 Profit T » 1001 1 NH Ph 66% 164 ° C 1002 1 NH neta-toli L 62% 174 ° C 1003 1 CH2 Ph 46% 125 ° C 1004 1 NH para — toli l 13% 162 ° C 1005 1 CH2 2-thienyl 49,5% 134 ° C 1006 1 NH ' l-f1uoroPh 30% 162 ° C 1007 1 NH 1 l ortho-toli1 38% 162 ° C 1008 0 - and 1 iso-propyl 60,5% 146 ° C 1009 1 NH 1 3 — chloroPh 32% 78 ° C 1010 1 NH I i tert-thiobuty 1 18% 120 ° C 1011 1 NH 1 4 — chloroPh 24% 196 ° C 1012 1 NH 1 2-chloroPh 69% 172 ° C 1013 0 l | piperidino 32% 206 ° C 1014 1 NH 4 r -1- -methoxyPh 27% 146 ° C 1015 1 NH 2 1 —MethoxyPh 29% 214 ° C 1016 1 CH2 2 — F ur 39% 105 ° C 1017 1 NH Aceti1 42% 200 ° C 1018 1 NH 4-NO0-Ph 41% 234 ° C 1019 1 NH 2-Pyridyl 60% 80 ° C 1020 1 NH 1 1-i- 3-pyrides1 17%

EXAMPLE .10; Preparation of compound 2 PO p.QS..top

Dissolve 11.1 g (50 mmol) of methyl 2-isothiocyanato-2-phenyl propionate in 150 ml of anhydrous tetrahydrofuran. A solution of 5.4 g (50 mmol) of phenyl hydrazine and 50 ml of anhydrous tetrahydrofuran was gradually added over 10 minutes: the temperature of the mixture was raised to 35 ° C. After the addition is complete, the reaction is allowed to react at 30 ° C for half an hour then the mixture is cooled to -5 ° C. At this temperature, a solution of 5.6 g (50 mmol) of potassium tert-thiobutylate and 50 ml of anhydrous tetrahydrofuran was added: the mixture turned purple and then a precipitate formed. Allow to react for half an hour at 0 ° C then add 8.5 g (60 mmol) of methyl iodide. Leave to react for 1 hour at room temperature. The mixture was diluted with 200 ml of ethyl acetate. The mixture is then washed twice with 150 ml of water each. The solution was dried over magnesium sulfate and then treated with activated charcoal. Concentrate: A brownish-purple honey is obtained which allows it to crystallize into 50 ml of ether. The precipitate was washed and then dried in vacuo. The rest of the product is obtained by concentrating the stock solutions and collecting the residual with 50 ml of diisopropyl ether. 12 g (yield = 77%) of 4-methyl-2methylthio-4-phenyl-1-phenylamino 2-imidazolin-5-one (compound 9) are thus obtained as a very light brown powder which melts at 149 ° C.

In the manner described above, the following compounds were obtained:

St. R'l R2 R3 B R4 1 ^Tl 58 - Me MeS NH 2 -, , 3— (Me) is Ph 116 ° C 67 4 Me ' MeS (CH2) 2 Ph miel 76 - Me MeS CH2 5 — pyrides l 67 ° C 77 - Me MeS CH2 t 2-pyridyl myel 78 - Me MeS N PhCH = 95 ° C 83 4-Me Me MeS NH Ph 179 ° C 84 - Me MeS NH 3 -Me-2-Pi r 148 ° C 85 4-CI Me MeS NH Ph 173 ° C 86 3 »4— (MeO) _: “Me MeS NH Ph 165 ° C 87 3 , 4- (MeO) with Me MeS NH 2-Me-Ph 151 ° C 88 4-Me Me MeS NH 2-Me-Ph 52 ° C 89 4-PhO Me MeS NH Ph 146 ° C 90 4-CI Me MeS NH 3 —Me — 2 — Pi r 133 ° C 91 4-CI Me MeS NH ..... ' 2-pyrides ¹ 1 172 ° C 92 R _x —PhCHz Me MeS NH Ph 166 ° C 93 4-PhO Me MeS NH 2-Me-Ph 130 ° C 94 4-F Me MeS NH 2-Me-Ph 120 ° C 96 4-CI Me MeS NH 2-Cl-Ph 145 ° C 97 - (CH2) 3 MeS NH Ph 158 ° C 98 - (CH2) 2 MeS NH Ph 85 ° C 99 4-CI H MeS NH 4-Cl-Ph 163 ° C 100 4-CI Me MeS NH 4-Cl-Ph 172 ° C 101 4-CI Me MeS NH 4-F-Ph 170 ° C 102 4-CI Me MeS NH 3-Cl-Ph 146 ° C 103 4-CI Me MeS NH 4-Me-Ph 178 ° C 104 - (CH2) 3 MeS NH 2-Cl-Ph 168 ° C 105 4-CI Me MeS NH 2-Me-Ph 124 ° C 106 4-CI Me MeS NH 3-Me-Ph 136 ° C

107 4-F Me MeS NH 3-Me-Ph 121 ° C 108 - Me MeS NH 3-F-Ph 163 ° C 109 Me MeS NH 2,5-F2-Ph 141 ° C 110 4-Me Me MeS NH 4-Cl-Ph 168 ° C 111 4-Me Me MeS NH 2-Cl-Ph 168 ° C 112 - (CH2) 3 MeS NH 4-Cl-Ph 191 ° C 113 - (CH2) 3 MeS NH 2-Me-Ph 174 ° C 114 4-Me Me MeS NH 3-Cl-Ph 184 ° C 115 4-F Me MeS NH 3-Cl-Ph 124 ° C 116 4-Me Me MeS NH 4-F-Ph 186 ° C 117 4-Me Me MeS NH 4-Me-Ph 157 ° C 118 4-F Me MeS NH 4-Me-Ph 158 ° C 119 4-Me Me MeS NH 3-Me-Ph 178 ° C 121 4-F Me MeS NH 4-Cl-Ph 159 ° C 121 4-F Me MeS NH 4-Cl-Ph 159 ° C 122 - Me MeS NH 2, 4- (Me) ₂ - Ph 63 ° C 123 Me MeS NH 3 -Cl-2-Pi r 127 ° C 124 4-C1 Me MeS NH 2-F-Ph 120 ° C 125 4-F Me MeS NH 2-F-Ph 112 ° C 126 4-Me Me MeS NH 2-F-Ph 156 ° C

EXAMPLE Utilization of 4-phenyl-4-methyl-1- (phenylthio) -2-methylthio].

A solution of 0.6 g (2.7 mmol) of 2-methylthio-4-methyl-4-phenyl-2-imidazolin-5-one in 50 ml of anhydrous tetrahydrofuran (THF) was added to a three-necked flask of 100 ml volume in an inert atmosphere. ). It was stirred on a magnetic stirrer and cooled to 0 ° C (ice + acetone bath). 0.30 g (1 molar ec33 equivalent of potassium tert-thiobutylate) was added and stirred for 10 min at 0 DEG C. Then a solution of 0.40 g of phenylsulfenyl chloride and 10 ml of anhydrous THF was poured. Allow the mixture to rise to room temperature. The reaction mixture was poured into 100 ml of water, extracted with 100 ml of ethyl acetate, the organic phase was washed 4 times with water and dried over sodium sulfate.

The organic phase was concentrated in vacuo. Yellow honey was obtained which crystallized from isorpopyl ether after purification on silica, yield 68% (melting point: 112 ° C).

EXAMPLE 12_l In vitro test:

The effect of the compounds of the invention on the following fungi responsible for diseases of cereals and other plants were studied:

Fusarium oxysporum f.sp. melonis

Rhizoctonia schoolchildren AG4

Helminthosporium gramineum Pseudocercosporella herpotrichoides

Alternaria alternata

Septoria nodorum

Fusarium roseum

Pythium rostratum Pythium vexans

For each test, proceed as follows: Pour nutrient medium made from potatoes, glucose and gelose (PAD medium) when melted into a Petri dish (100 ml per bowl) after being sterilized in an autoclave at 120 ° C. .

In the course of filling, Petri dishes are injected into the still liquid medium with an acetone solution of the active substance to obtain the desired final concentration.

As controls, we take Petri dishes analogous to the previous ones, into which we pour similar amounts of nutrient medium that does not contain the active substance.

After 24 hours, each Petri dish was seeded by laying a portion of the ground mycelium of a previous culture of the same fungus.

The Petri dishes are allowed to stand for 5 days at 20 ° C and then the growth of the fungus in Petrijevci containing the active substance under test is compared with the growth of the same fungus in Petrijevka used as a control.

In this way, the inhibition rate for each compound tested is 20 ppm.

Thus we obtain the following results:

Good activity, ie a degree of inhibition of the fungus between 80% and 100% was detected 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 Rhizoctonia schoolchildren.

- compounds 16 and 26 for Pseudocercosporella herpotrichoides.

- compounds 11, 16 and 26 for Septoria nodorum.

- Compounds 9, 11, 16 and 26 for Helminthosporium grams not um.

PRIMEE. 13; In vivo test on Plasmopara viticola (pepelas.ta pl £ 2 £ n vines):

Prepare, by fine grinding, an aqueous suspension of the active substance to be tested, of the following composition:

- Active substance: 60 mg

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

- Make up to 60 ml with water.

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

Vines (Vitis vinifera) seedlings, a Chardonnay variety, are grown in pots. When these plants are 2 months old (stage 8 to 10 leaves, height 10 to 15 cm), they are sprayed with the aforementioned aqueous suspension.

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

After drying for 24 hours, contaminate each plant by spraying the aqueous suspension of Plasmopara viticol spores prepared with a 4-5 day old culture so that the suspension contains 100,000 units per cm ³ .

Contaminated plants are then incubated for two days at about 18 ° C, saturated with moisture in the atmosphere and then for 5 days at about 20-22 ° C and 90-100% relative humidity.

Results are read 7 days after contamination compared to control plants.

Under these conditions, at a dose of 1 g / l, good protection (at least 75%) or complete with the following compounds was observed: 1, 2, 9, 10, 12, 13, 15, 16, 18, 20, 22, 23, 24, 25, 30, 31, 34, 35, 37, 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 Test la vivo on Puccinia recondita 1 cereal); Prepare, by fine grinding, an aqueous suspension of the active substance to be tested, of the following composition:

- Active substance: 60 mg

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

- Make up to 60 ml with water.

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

Wheat in pots sown on a mixture of peat and soil (terre pouzzolane) 50/50 is treated at a 10 cm height by spraying the aforementioned aqueous suspension.

Spray the wheat spore suspension (100,000 sp / cm ³ ) after 24 hours on wheat; this suspension was obtained from contaminated plants. Then the wheat is placed for 24 hours in an incubation cell at about 20 ° C and 100% relative humidity, and then for 7 to 14 days at 60% relative humidity.

The control of the condition of the plants is performed between eight and fifteen days after contamination, by comparison with the untreated control plant.

Under these conditions, at a dose of 1 g / l, good protection (at least 75%) or complete with the following compounds is observed: 2, 9, 10,

15, 18, 20 to 23, and 39, 55, 57, 64, 68, 75, 83 to 90, 93,

94, 98.

EXAMPLE 15j_ Test in vivo. on Phvtophthoza infestans (a foamy mold of tomato

Prepare, by fine grinding, an aqueous suspension of the active substance to be tested, of the following composition:

- Active substance: 60 mg

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

- Make up to 60 ml with water.

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

Tomato plants (Marmonde variety) are grown in pots. When the plants are one month old (stage 5 to 6 leaves, height 12 to 15 cm), they are treated by dispersing the aforementioned aqueous suspension and by varying concentrations of the compound being tested.

After 24 hours, we contaminate each plant by spraying an aqueous suspension of Phytophtora infestans (30000 sp / cm ³ ).

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

Seven days after contamination, the results obtained in the case of plants treated with the active substance are compared with those obtained in the case of the plants used as controls. Under these conditions, a dose of 1 g / l to bro protection (at least 75%) or complete with the following compounds is observed: 2, 9, 15, 30, 39, 45, 55, 68, 75, 84, 85, 90, 94 , 98,

107, 108.

These results clearly demonstrate the good fungicidal properties of the derivatives of the invention against fungal diseases of plants that are caused by fungi belonging to a wide variety of families such as Phycomycetes, Basidomycetes, Ascomycetes, Adelomycetes or Fungi imperfecti, in particular the ash mold of the vine, the ash and the tomato mildew .

In the practical use of the compounds of the invention it is rarely used alone. Most often, these compounds are part of the compositions. These compositions, useful as fungicidal agents, contain as an active substance one compound of the invention previously described, in admixture with a solid or liquid carrier acceptable in agriculture and surfactants equally acceptable in agriculture. Inert and conventional carriers and conventional surfactants are particularly useful. These compositions are also part of the invention.

These compositions may also contain all kinds of other ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants, etc. More generally, the compounds used in the invention may be combined with all of the solid or liquid additives according to conventional molding techniques.

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

In this explanation, the term carrier means an organic or inorganic substance, natural or synthetic, with which a compound has been combined to facilitate its application to a plant, seed or soil. This carrier is therefore usually inert and must be acceptable in agriculture, especially on the plant under cultivation. The carrier may be solid (clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water; alcohols, in particular butanol, etc.).

Surfactants may be an emulsifying, dispersing or wetting agent of the ionic or non-ionic type, or a mixture of such surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide on fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols, or arylphenolate sulfinolenate) ), phosphate esters of polyoxyethylated alcohols or phenols, fatty acid and polyol esters, sulfate functional derivatives, sulfonates and phosphates of precursors. The presence of at least one surfactant is usually essential when the compound and / or inert carrier is insoluble in water and if the application vector is water.

Thus, compositions for agricultural use according to the invention may contain the active substances of the invention within very wide limits, from 0.05% to 95% (by weight). The preferred content of surfactant in them is in the range from 5% to 40% by weight.

These compositions of the invention are in substantially different forms, solid or liquid.

Dust powders (with a concentration of up to 100% compound) and granules, in particular those obtained by extrusion, compacting, impregnation of a granular carrier, powder granulation (the concentration of the compound in these granules is between 0.5 and 80% for the latter cases), tablets or effervescent tablets.

The compounds of formula (I) can be used in powder form; a composition containing 50 g of the active substance and 950 g of talc may also be used; we can also use a composition containing 20 g of active substance, 10 g of finely divided silica and 970 g of talc; these ingredients are mixed and ground and the mixture is applied by dusting.

Solvents, in particular water soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or dispersing powders) may be mentioned as forms of liquid compositions or those intended for the assembly of liquid compositions upon application. , pastes, gels.

Concentrates that can be emulsified or dissolved most often contain 10 to 80% of the active substance, and emulsions or solutions ready for use contain 0.001 to 20% of the active substance.

In addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% of suitable additives, such as stabilizers, surfactants, penetrating agents, decay inhibitors, colorants or the aforementioned adhesives.

From these concentrates, dilutions with water can be used to prepare emulsions of any desired concentration, which are particularly suitable for application on cultures.

As an example, here is the composition of some concentrates that can be emulsified:

EXAMPLE £ E 1:

- active substance 400 g / i - Alkali dodecylbenzene - Oxyethylated nonylphenol z sulfonate 10 molecules 24 ethylene oxide 16 g / i - cyclohexanone 200 g / i - aromatic solvent complete to 1 1

According to another emulsifiable concentrate formula, we use:

EXAMPLE ΏΕ 2

- active substance 250 g / l

- epoxidized vegetable oil 25 g / l

- a mixture of alkylaryl sulfonate and polyglycol ether and fatty alcohols 100 g / l

- dimethylformamide 50 g / l

- xylene 575 g / l

Concentrated suspensions, which can equally be used by spraying, are prepared in such a way as to obtain a liquid, stable, non-settling product and typically contain from 10 to 75% of the active substance, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives such as anti-foam agents, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or some organic liquid in which the active substance is low soluble or insoluble: some solid organic sub-substances or inorganic salts can be dissolved in the carrier to help prevent sedimentation, or as anti-freezing agents.

As an example, here is the composition of one concentrated suspension:

EKIMEE 1:

- active substance 500 g

- phosphate of polyethoxylated tristyrylphenol 50 g

- polyethoxylated alkylphenol 50 g

- sodium polycarboxylate 20 g

- Ethylene glycol 50 g

- Organopolysiloxane oil (anti-foam) 1 g

- polysaccharide 1.5 g

- water 316,5 g

Wettable powders (or dusting powders) are usually prepared in such a way that they contain 20 to 95% of the active substance and typically contain, in addition to the solid carrier, 0 to 30% of a wetting agent, 3 to 20% of a dispersing agent, and, where necessary, from 0.1 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, clotting agents, colorants, etc.

In order to obtain powders or wettable powders, the active substances in suitable mixers with additional substances are well mixed and ground in mills or other suitable grinders. In this way, spray powders are prepared which are advantageously wetted and suspended; they can be suspended in water at any desired concentration, and these suspensions can be used very favorably, especially for plant application.

Pastes can be used instead of wettable powders. The conditions and modalities for the realization and use of these traps are similar to those for wettable powders or spray powders.

Here are examples of different compositions of wettable powders (or spray powders):

EXAMPLE EM 1 = active substance ethoxylated fatty alcohol (wetting agent) ethoxylated phenylethylphenol (dispersing agent)

50%

2.5%

5% chalk (inert carrier)

42,5%

EXAMPLE £ M 2:

active substance

10% synthetic branched-type oxo alcohol ethoxylated at C ₁₃ with 8 to 10 ethylene oxides (wetting agent)

- neutral calcium lignosulfonate (dispersant)

0.75%

12%

- calcium carbonate (inert filling)

EXAMPLE RM 3:

This wetting powder contains the same ingredients in the walking case, in the following proportions:

- active substance

- wetting agent

- dispersant

- calcium carbonate (inert filling)

RRIMER RM 1:

- active substance

- ethoxylated fatty alcohol (wetting agent)

- ethoxylated phenylethylphenol (dispersing agent)

EXAMPLE £ M 5 .:

- active substance

- mixture of anionic and nonionic surfactants (wetting agent)

- Sodium lignosulfonate (dispersant)

- kaolin clay (inert carrier)

Aqueous dispersions and emulsions, for example compositions up to 100% as before 75%

1.5%

8% to 10 0%

90%

4%

6%

50%

2.5%

5%.

42.5% prepared by dilution with a water-wetting powder or emulsifiable concentrate according to the invention are encompassed by the general scope of the present invention. Emulsions can be water-oil or oil-in-water and may have a thick consistency such as that of mayonnaise.

The compounds of the invention can be formulated in the form of water-dispersible granules, equally covered by the invention.

These dispersible granules, visible densities, typically between about 0.3 and 0.6, have particle sizes typically between about 150 and 2000 and preferably between 300 and 1500. The active substance content of these granules is generally in the range of about 1% to 90%, preferably between 25% and 90%.

The remainder of the granule is primarily composed of a solid charge and possibly surfactant adjuvants, which add to the granule properties that allow it to be dispersed in water. These granules may in particular be of two types, differing in whether or not the filling is soluble in water. If the charge is hydro-solubility, it may be inorganic or, preferably, organic. Urea has been excellent. In the case of insoluble filling, it is preferably inorganic such as kaolin or bentonite. In this case, it is advantageous if it is combined with a surfactant (in the ratio of 2 to 2 0% by weight of the granule) of which more than half, for example, consists of at least one dispersing agent, in particular anionic such as an alkali or alkaline earth alkali polynaphthalene sulfonate or some alkali or alkaline earth lignosulfonate, the residue consists of non-ionic or anionic wetting agents such as alkali or alkaline earth

4Ί alkyl naphthalene sulfonate.

Alternatively, other adjuvants such as anti-foam agents may be added, although not necessary.

The granules according to the invention can be prepared by mixing the necessary ingredients, which are then granulated by various known techniques (apparatus for the preparation of dragees, fluid bed, atomizer, extrusion, etc.). Typically, we end up with crushing followed by screening at the particle dimension selected within the limits mentioned above.

In particular, it is prepared by extrusion, acting as indicated in the following examples.

EXAMPLE GD 1 Dispersion granules

In the mixer, 90% (by weight) of the active substance and 10% of urea in beads are mixed. The mixture is then ground in a crusher with wedges. A powder is obtained which is moistened with about 8% (by weight) of water. The wet powder is squeezed out in a perforation roller extruder. A granule is obtained which is dried, then crushed and sieved in such a way that only granules of dimensions in the range of 150 to 2000 m are left.

EXAMPLE GD2. _l Granules with & Dispersion

The following ingredients are mixed in the blender:

- active substance 75%

- wetting agent (sodium alkylnaphthalate 2% len sulfonate) dispersing agent (sodium (polynaphthalene sulfonate)

8%

- inert filler insoluble in water (kaolin) 15%

This mixture is granulated in a liquid layer in the presence of water, then dried, crushed and sieved in such a way that granules of dimensions ranging from 0.15 to 0.80 mm are obtained.

These granules can be used alone, in solution or dispersion in water, to obtain the required dose. They can also be used to form associations with other active substances, in particular fungicides, the latter being in the form of wettable powders or granules or aqueous suspensions.

Regarding compositions adapted for storage and transport, those containing from 0.5 to 95% (by weight) of the active substance are most preferred.

It is an object of the invention to use the compounds of the invention to combat fungal diseases of plants by preventing or treating them or their place of birth.

Preference is given to administering these compounds at doses of 0.005 to 5 kg / ha and more specifically 0.01 to 1 kg / ha.

RHONE-POULENC AGROCHIMIE:

(, ·. -J t (I)

Ib '

(Π)

R ₂ .

Rf

/ SCH ₃

N = CC ^x sch ₃ co ₂ h (UD

R ₄ - (3) n — NHi (TV)

R, ^ _c; ^SCH 'sch ₃

Rf C-NH- (B) n-R,

Oh

CO., LTD

R ₂

Ri-C-xN = C = S co ₂ r (Vni).

Claims (38)

PATENT APPLICATIONS 1) Compounds having an imidazolinone or imidazolintion group, characterized in that they conform to general formula (I): where: - W is a sulfur or oxygen atom or an S = O group. - A is O or S - n = 0 or 1 - B is N (R ₅ ) or O or S or C (R ₅ ) (R ₆ ) or SO ₂ or C = O. - R ^ and R ₂ , the same or different, are: - H, provided that one of the two groups is other than H, or an alkyl or haloalkyl radical having 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radicals having 2 to 6 carbon atoms, or a dialkylaminoalkyl or cycloalkyl radical of 3 to 7 carbon atoms, or - an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl optionally substituted by 1 to 3 groups selected from R ₇ or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl being defined above, or - R 1 and R ₂ may form, to the ring-linked carbon, a carbocyclic or heterocycle having 5 to 7 atoms, these rings may be combined with phenyl optionally substituted by 1 to 3 groups selected from R ₇ ; - ^R 3 an alkyl group of 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, Ν-dialkylcarbamoylalkyl group having 4 to 8 atoms or - an arylalkyl group, the alkyl moiety being the radical z 1 to 6 carbon atoms, the aryl moiety being phenyl, thienyl, furyl, pyridyl optionally substituted by 1 to 3 groups selected from R ₇ ; * R ₄ 3θ: a hydrogen atom when n is 1 or an alkyl group of 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, dial-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms or - an aryl radical comprising phenyl, naphthyl, thienyl, furyl pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl optionally substituted by 1 to 3 groups selected from R ₇ or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl being as defined above, or - an amino group disubstituted with 2 identical or different groups selected from: - an alkyl radical of 1 to 6 carbon atoms, - alkoxyalkyl, alkenyl or alkynyl radicals having 3 to 6 carbon atoms, - cycloalkyl radical of 3 to 7 carbon atoms, - an arylalkyl radical such as defined above, phenyl or naphthyl optionally substituted by 1 to 3 groups selected from R _7, or - thienylmethyl or furfuryl radical, - a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted by alkyl having 1 to 3 carbon atoms; ^R 5 ^ ' ^e: - H, unless R _{4 is} H, or - alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl having 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloalkyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl, cyanoalkylsulfonyl having 2 to 6 carbon atoms, or - alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl radical of 3 to 6 carbon atoms, or - formyl radical, or - cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl, alkynylcarbonyl radical of 3 to 6 carbon atoms, or - a cycloalkylcarbonyl radical having 4 to 8 carbon atoms, or - phenyl radical; arylalkylcarbonyl, in particular phenylacetyl and phenyl propionyl; arylcarbonyl, in particular benzoyl, optionally substituted with 1 to 3 groups selected from R _7; thienylcarbonyl; furicarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or phenylthiolcarbonyl, the phenyl itself being optionally substituted with 1 to 3 groups selected from R ₇ ; alkylthiolcarbonyl; haloalkylthiocarbonyl; alkoxyalkylthiolcar bonyl; cyanoalkylthiocarbonyl; benzylthiocarbonyl; furfurylthiocarbonyl; tetrahydrofurfurylthiolcarbonyl; thienylmethylthiol carbonyl; pyridylmethylthiolcarbonyl; or arylsulfonyl or - carbamoyl radical, possibly mono or substituted with an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - phenyl optionally substituted by 1 to 3 groups R ₇ ; - sulfamoyl group, possibly mono or disubstituted by an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - phenyl optionally substituted by 1 to 3 groups R ₇ ; - an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or a cycloalkylsulfonyl group of 3 to 7 carbon atoms; - ^r 6 3θ ^: - a hydrogen atom or - cyano group or an alkyl group of 1 to 6 carbon atoms or cycloalkyl of 3 to 7 carbon atoms, or an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms, or - a benzoyl group optionally substituted by 1 to 3 R ₇ groups; -R _? is: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms, or - cycloalkyl, halocycloalkyl, alkenyloxy, alkinyloxy, alkenylthio, alkynylthio radicals having 3 to 6 carbon atoms, or - a nitro or cyano group, or - an amino radical optionally mono or substituted with an alkyl or acyl radical of 1 to 6 carbon atoms or alkoxycarbonyl of 2 to 6 carbon atoms, or - a phenyl, phenoxy or pyridyloxy radical, these radicals being optionally substituted; and their salts, with the exclusion of compounds in which B is where R ^ and R ₂ are simultaneously phenyl or simultaneously methyl, C (R ^) (R), A is sulfur and W is 0 or S; by excluding 3 compounds with R ^ = hydrogen, n = 1, B = NR ₅ , with R ^ and R ₄ = methyl, AR ₃ = SCH3, wherein W = O and R _{2 are} hydrogen, methyl or phenyl; the same by excluding a compound in which R 1 is phenyl, R ₂ , R ₃ and R ₄ are methyl, n is zero and A and W are both sulfur atoms. 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 in that they conform to the general formula: in which W, n, R ^ to Rg have the same meaning as in claim 1 5) Compounds according to claim 2, characterized in that they conform to the general formula: wherein W, R to R ₅ have the same meaning as in claim 1. 6) Compounds according to claim 2 of the general formula: characterized in that B, n R-j_ to R _{4 have the} same meaning as in claim 1. Compounds according to claim 2, characterized in that they correspond to the general formula Id wherein B, n, R to R ₄ have the same meaning as in claim 1 Compounds according to one of claims 1 to 7, characterized in that R8 is a hydrogen atom. 9) Compounds according to claim 5, characterized in that R _{5 is} a hydrogen atom (compound Ib '). Compounds according to one of claims 1 to 9, characterized in that R 1 and R _{2 are} other than hydrogen atoms. Compounds according to any one of claims 1 to 10, characterized in that R _{2 is an} alkyl group of 1 to 3 carbon atoms. Compounds according to one of Claims 1 to 11, characterized in that R 6 is phenyl optionally substituted by the group R ₇ . Compounds according to any one of claims 1 to 12, characterized in that the alkyl group is from 1 to 3 carbon atoms. Compounds according to any one of claims 1 to 13, characterized in that R _{4 is} phenyl optionally substituted by one group R ₇ . Compounds according to one of claims 1 to 14, characterized in that R _{3 is a} methyl radical. 16. A process for the preparation of compounds of formula (I) according to claim 2, characterized in that S-alkylation of the 2-thiohydantoins of formula (II) is carried out with a compound of formula R ₃ X, in the presence of a base, which is filtered as follows: Base Solvent W (Π) wherein R ₁ , R ₂ , R ₃ , R ₄ , B and W have the meaning as in claim 1 and X is a chlorine atom, bromine, iodine, or sulfate group, or an alkylsulfonyloxy or arylsulfonyloxy group. 17. A process for the preparation of compounds of 2-methylthio-2-imidazolin5-ones of formula (Ic) according to claim 6, characterized in that cyclization of the compound of formula (V) is carried out by simple heating in an aromatic solvent at reflux: <5CH ₃ ² \ / SCH ₃ FC-NH- (B) n-R ₄ O (V) in which R _l, R _2, tevku first R ₄ , B and n have the same meaning as in Claims A process for the preparation of compounds of formula (V) according to claim 17, characterized in that the condensation of iminodithiocarbonate of formula (III) with an amine or hydrazine of formula (IV) is carried out according to the scheme: n = c ( ^sch 3 ^ sch ₃ CO-> H R ₄ - (B) n — NH ₂ (IV) _r r ₂ . R (ΙΠ)> SCH ₃ SCH ₃ , C — ΝΉ— (B) n— R'4 o (V) 'X in which R _{1z has} R ₂ , R ₄ , B and n have the same meaning as in claim 1, and the acid (III) must be activated for this condensation in the form of acid chloride, dicyclohexylisourea with dicyclocarbodiimide or imidazole with carbonyldiimidazole. A process for the preparation of compounds of formula (Ib) according to the scheme: 19) characterized in that a reaction is carried out in a solvent in the presence of a base of a compound of formula R 1 X with a compound of formula (Ib) according to claim 5, wherein the group R _{5 is} a hydrogen atom according to claim 9 (compound Ib '), of group R 1 to R ₄ have the meaning given in claim 1, the group R ₅ is an alkyl, alkoxycarbonyl, acyl, aryl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl group and X is a leaving group such as a halogen, sulfate group, phenoxy optionally substituted, R ₅ O in the case of R _{5 being} acyl, or an alkylsulfonyloxy or arylsulfonyloxy group or a leaving group such as isocyanate or isothiocyanate. 20) A process for the preparation of compounds of formula (Id), according to the scheme: / characterized in that a compound of formula (Id) reacts according to claim 7, wherein R _{2 is} a hydrogen atom (compound (Id ')) with a compound of formula R ₂ X in a solvent and in the presence of a base, at a temperature in the range of -30 ° C to + 80 ° C, wherein X is a chlorine, bromine or iodine atom and R _x to R, B and n have the same meaning as in claim 1. 21. The process of claim 20, wherein the base is selected from the group comprising an alcoholate, a metal hydride, or an amine, and the solvent is selected from the group consisting of ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents. 22) A process for the preparation of compounds of formula (I) according to claim 1, wherein W is a group S = 0, characterized in that the S-oxidation of the compound of formula (I) in which W is a sulfur atom, and this oxidation is 2-imidazoline The 5-thion is achieved by stoichiometric amounts of peroxides in the solvent at a temperature in the range of -20 ° C to + 20 ° C. Process 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) Process for the preparation of the dithiohydantoins of formula (VI): H (VD in which R _{1 #} R ₂ and R _{4 have the} same meaning as in claim 1, characterized in that two isothiocyanates react, one of these two cannot become an anion whose formulas are R ₁ R ₂ CHNCS and R ₄ NCS, in the presence of a base, in a solvent and at a temperature lower than -60 ° C. A process according to claim 24, wherein the base is selected from potassium tert-thiobutylate, sodium or lithium bis bis (trimethylsilyl) amine salt and / or alkali hydrides, and the solvent is selected from ethers and cyclic ethers. A process according to any one of claims 24 or 25, characterized in that R ₃ and / or R ₂ are an electron attracting group such as aryl, substituted aryl or alkoxycarbonyl. Process according to one of Claims 24 to 26, characterized in that the isothiocyanate R _{4 of the} NCS which cannot become anion is aryl isothiocyanate. 28) Process for the preparation of 2-thiohydantoins of formula (VII): (vn) characterized in that, before cyclization, the compound of formula (IV) R ₄ (B) _n NH _{2 is} reacted with isothiocyanates which are derivatives of amino acids of formula (Vlyl): R, r Č_N = C = S ¹ I CO, R (VITI) where R ^, R ₂ R ₄ , B and n have the same meaning as in claim 1. Process according to claim 28, characterized in that the cyclization is carried out thermally by heating the mixture of reagents at this temperature in the range from 110 to 18 ° C in an aromatic solvent such as toluene, xylene, chlorobenzenes. Process according to claim 28, characterized in that the cyclization is carried out with a base equivalent, in a solvent and at a temperature in the range of -10 to + 80 ° C, and then the reaction mixture is neutralized at room temperature. The process of claim 30, wherein the base is selected from the group consisting of an alkali alcoholate, an alkali hydroxide or a tertiary amine; the solvent is selected from the group consisting of ethers, cyclic ethers, alcohols, esters, DMF, DMSO. 32) The method according to claims 28 and 30, characterized in that, before the target of the 2-thiohydantoin derivatives is achieved by neutralizing the acidic reaction mixture, the alkyl halide R ₃ X is stimulated to form a compound of formula Id, wherein X is a chlorine, bromine or iodine atom , or the group alkylsulfonyloxy or arylsulfonyloxy and R ₃ has the same meaning as in claim 1. 33) Compounds useful primarily as intermediates in the preparation of compounds according to claims 1 to 15, characterized in that they correspond to formulas II, III, IV, V, VI, VII and VIII. ^Ri y ⁿ Y ^s (B) n - R ₄ Rj. K, 'co ₂ hw (Π) (ΠΙ) sch ₃ sch ₃ R ₄ - (3) n — NH ₂ (IV) r, K = <y ^SCH SCH, Rf C-NH- (B) n-R. (Ύ) R ₁ -CN = C = S CO.R (VIII). 34) Fungicidal compositions, characterized in that they contain, combined with one or more solid or liquid carriers acceptable in agriculture and / or surfactants equally acceptable in agriculture, one (or more) active substances which are a compound of formula I: (I) where: - W is a sulfur or oxygen atom or an S = 0 group. - A is O or S - n = 0 or 1 - B is N (R ₅ ) or O or S or C (R ₅ ) (R ₆ ) or S0 ₂ or C = O. - R · ^ and R ₂ , the same or different, are: - H, provided that one of the two groups is other than H, or an alkyl or haloalkyl radical having 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radicals having 2 to 6 carbon atoms, or a dialkylaminoalkyl or cycloalkyl radical of 3 to 7 carbon atoms, or - an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl optionally substituted by 1 to 3 groups selected from R ₇ or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl being defined above, or - R 1 and R ₂ may form, to the ring-linked carbon, a carbocycle or heterocycle having 5 to 7 atoms, these rings may be combined with phenyl optionally substituted by 1 to 3 groups selected from R ₇ ; - ^R 3 ^3e: an alkyl group of 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, Ν-dialkylcarbamoylalkyl group having 4 to 8 atoms or - an arylalkyl group, the alkyl moiety being the radical z 1 to 6 carbon atoms, the aryl moiety being phenyl, thienyl, furyl, pyridyl optionally substituted by 1 to 3 groups selected from R ₇ ; -R ₄ is: a hydrogen atom when n is 1 or an alkyl group of 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, dial-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms or - an aryl radical comprising phenyl, naphthyl, thienyl, furyl pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl, or methylene dioxyphenyl optionally substituted by 1 to 3 groups selected from R ₇ or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl being as defined above, or - an amino group disubstituted with 2 identical or different groups selected from: - an alkyl radical of 1 to 6 carbon atoms, - alkoxyalkyl, alkenyl or alkynyl radicals having 3 to 6 carbon atoms, - cycloalkyl radical of 3 to 7 carbon atoms, - an arylalkyl radical such as defined above, phenyl or naphthyl optionally substituted by 1 to 3 groups selected from R _7, or - thienylmethyl or furfuryl radical, - a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted by alkyl having 1 to 3 carbon atoms; ' ^R 5 3 ^e: - H, unless R _{4 is} H, or - alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl having 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloalkyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl, cyanoalkylsulfonyl having 2 to 6 carbon atoms, or - alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl radical of 3 to 6 carbon atoms, or - formyl radical, or - cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl, alkynylcarbonyl radical of 3 to 6 carbon atoms, or - a cycloalkylcarbonyl radical having 4 to 8 carbon atoms, or - phenyl radical; arylalkylcarbonyl, in particular phenylacetyl and phenyl propionyl; arylcarbonyl, in particular benzoyl, optionally substituted with 1 to 3 groups selected from R _7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxy68 carbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or phenylthiolcarbonyl, the phenyl itself being optionally substituted with 1 to 3 groups selected from R ₇ ; alkylthiolcarbonyl; haloalkylthiocarbonyl; alkoxyalkylthiolcar bonyl; cyanoalkylthiocarbonyl; benzylthiocarbonyl; furfurylthiocarbonyl; tetrahydrofurfurylthiolcarbonyl; thienylmethylthiol carbonyl; pyridylmethylthiolcarbonyl; or arylsulfonyl or - carbamoyl radical, possibly mono or substituted with an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - phenyl optionally substituted by 1 to 3 groups R ₇ ; - sulfamoyl group, possibly mono or disubstituted by an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - phenyl optionally substituted by 1 to 3 groups R ₇ ; - an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or a cycloalkylsulfonyl group of 3 to 7 carbon atoms; ' ^r 6 3 ^e: - a hydrogen atom or - cyano group or an alkyl group of 1 to 6 carbon atoms or cycloalkyl of 3 to 7 carbon atoms, or an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms, or - a benzoyl group optionally substituted by 1 to 3 R ₇ groups; -R ₇ is: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms, or - cycloalkyl, halocycloalkyl, alkenyloxy, alkinyloxy, alkenylthio, alkynylthio radicals having 3 to 6 carbon atoms, or - a nitro or cyano group, or - an amino radical optionally mono or substituted with an alkyl or acyl radical of 1 to 6 carbon atoms or alkoxycarbonyl of 2 to 6 carbon atoms, or - a phenyl, phenoxy or pyridyloxy radical, these radicals being optionally substituted; and salts thereof. 35) Fungicidal compositions according to claim 34, characterized in that they contain from 0.5% to 95% by weight of the compounds according to one of claims 1 to 15. 36) A method of treating cultures that are diseased or susceptible to fungicidal diseases, characterized in that they administer, in a preventive or therapeutic manner, an effective amount of a compound according to one of claims 1 to 15 or a composition according to claims 34 or 35. The method of treatment of claim 36, wherein the effective dose is in the range of 0.005 to 5 kg / ha. 38) The treatment method of claim 37, wherein the effective dose is in the range of 0.01 to 1 kg / ha.