SK375392A3 - 2-imidazoline-5-on and 2-imidazoline-5-tion derivatives, method of their preparation and fungicidal agents containing these 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

Technical field

The present invention relates to novel imidazolinone and imidazolinethione compounds which are useful in the protection of plants against fungal plant diseases. The invention also relates to processes for the preparation of said imidazolinone and imidazolinthione compounds, as well as a product which may optionally be used as intermediates in these preparative processes. The invention further relates to the use of said imidazolinone and imizazolinthionic compounds as fungicides. The invention also relates to fungicidal compounds and fungicidal compositions consisting of or containing said imidazolinone and imidazolinthionic products. The present invention is ultimately directed to methods of combating fungal crops diseases using said novel imidazolinone and imidazolinthione compounds or using said fungicidal compositions comprising said imidazolinone and imidazolinthione products.

SUMMARY OF THE INVENTION

It is an object of the invention to provide compounds which have improved properties in combating fungal plant diseases. Another object of the invention is to provide compounds which will have an improved application spectrum in the field of fungal plant diseases.

It has now been found that these objectives can be achieved by the product of the invention which are 2-imidazolin-5-one or 2-imidazoline-5-thione derivatives of the general formula I

7th

in which

W is S or O or S = O,

A is oxygen or sulfur, n is 0 or 1,

B is NR @ 4 or an oxygen or sulfur atom or CR @ 1 --R @ 8 or SC @ 4 or C = O,

R and R R, which are the same or different, represent a hydrogen atom, provided that one of the two groups is different from the hydrogen atom, or an alkyl or haloalkyl group containing 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or an alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkyl or cycloalkyl group having 3 to 7 carbon atoms or an aryl group comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinoline or methylenedioxyphenyl, each of which may be optionally substituted with 1 to 3 groups selected from the group consisting of or arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl in which: an aryl and alkyl radical as defined above; or

R 2 and R ₂ together with the carbon atom to which they are attached may form a carbocyclic or heterocyclic group of 5 to 7 atoms, which groups may be fused to a phenyl ring optionally substituted with 1 to 3 groups selected from R 6,

R 3 represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or 6-alkoxycarbonylalkyl group or N

N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an arylalkyl group in which the alkyl radical contains up to 6 carbon atoms and the aryl radical is a phenyl, naphthyl, thienyl, furyl or pyridyl group, optionally substituted with 1 to 3 groups selected from .

R 1 represents a hydrogen atom when n is 1, or an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or Nalkylcarbonylalkyl group Or 3 to 6 carbon atoms;

N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or a methylenedioxyphenyl group, each of which may be optionally substituted with 1 to 3 groups selected from the group consisting of or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group in which the aryl and alkyl radicals are as defined above, or an amino group disubstituted by two identical or different groups selected from the group consisting of alkyl having 1 to 6 carbon atoms, alkoxyalkyl, alkenyl or alkynyl having 3 to 6 carbon atoms, cycloalkyl for a group containing 3 to 7 carbon atoms, an arylalkyl group as defined above, a phenyl group or a naphthyl group, optionally substituted by 1 to 3 groups selected from R?, or a thienylmethyl or furfuryl group, a pyrrolidine, piperidine, morpholine or piperazine group, optionally substituted alkyl having 1 to 3 carbon atoms,

R _c is

D is hydrogen, except when it is hydrogen, or an alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl or alkoxyalkylsulfonyl group C 6 -C 6 alkoxy or alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl having 3 to 6 carbon atoms or a formyl group or cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl having 3 to 6 carbon atoms; 6 carbon atoms or a cycloalkylcarbonyl group having 4 to 8 carbon atoms or phenyl group, As the aryl group is particulary on phenylacetyl and phenylpropionyl, arylcarbonyl, in particular benzoyl, optionally substituted with 1 to 3 groups selected from the meaning of R _7, thienylcarbonyl, furyl group, pyridylcarbonyl, benzyloxycarbonyl, furfuryloxycarbonyl, tetrahydrofurfuryloxycarbonyl, thienylinethoxycarbonyl, pyridylmethoxycarbonyl, phenoxycarbonyl or (phenylthio) carbonyl, in which the phenyl radical optionally substituted by 1 to 3 of the alkyl radical is optionally substituted by 1 to 3; , (haloalkylthio) carbonyl, (alkoxyalkyithio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl, (furfurylthio) carbonyl, (tetrahydro furfurylthio) carbonyl, (thienylmethylthio) carbonyl, (pyridylmethylthio) carbonyl or arylsulfonyl or carbamoyl, optionally mono- or disubstituted groups selected from the group consisting of alkyl or haloalkyl of 1 to 6 carbon atoms or cycloalkyl, alkenyl or a group containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms or a phenyl group optionally substituted by 1 to 3 groups selected from R z, a sulfamoyl group, a sulfamyl group or a mono- or disubstituted group selected from the group consisting of alkyl or haloalkyl of 1 to 6 carbon atoms or cycloalkyl, alkenyl or alkynyl of 3 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl or C 2 -C 6 cyanoalkyl or a phenyl group optionally substituted by 1 to 3 groups selected from R 6, alkylthioalkylsulfonyl of 3 to 8 carbon atoms or cycloalkylsulfonyl of 3 to 7 carbon atoms,

R 1 is b

a hydrogen atom or a cyano or C 1 -C 6 alkyl or C 3 -C 7 cycloalkyl or C 2 -C 6 acyl or alkoxycarbonyl group or a benzoyl group optionally substituted by 1 to 3 groups selected from R .?.

R1 represents a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio-, haloalkylthio- or alkylsulfonyl group having 1 to 6 carbon atoms or a cycloalkyl, halo-cycloalkyl, alkenyloxy-, alkynyloxy-, alkenylthio- or alkynylthio- group containing 3 to 6 carbon atoms; a carbon atom or a nitro or cyano group or an amino group, optionally a mono- or disubstituted alkyl or acyl group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms, the phenyl, phenoxy or pyridyloxy group, which groups may be optionally substituted, and salts thereof.

Certain specific compounds of formula I are already known. Ternito compounds are compounds of formula Ia

wherein W, R 1 to R 8 and n are as defined in claim 1.

The delimited S-alkylated derivatives of 5,5-diphenyl-2-thiohydantoin and 5,5-diphenyldithiohydantoin have been studied in particular to determine their pharmacological properties:

a) Zejc A., Dissertation Pharmaceuticals and Pharmacology, Warsaw, 20 (5), 507-524 and 525-537 (1968);

(b) Lucka-Sobstel B. and Zejc A., Dissertions of Pharmaceutics and Pharmacology, 22 (1), 13-19 (1970),

(c) Fetter J., Harsanyi K., Nyitrai J. and Lempert K.

Acta Chemica (Budapest), 78 (3), 325-333 (1973).

No agricultural fungicidal activity has been reported with these compounds.

I

Other specific compounds of formula I have been described by Bohme, Martin and Strahl in Archiv der Pharmazie, 313, 10-15 (1900) (ref.d). These are three compounds of the general formula

wherein R represents either a hydrogen atom or a methyl group or a phenyl group.

These compounds are thus included in the compounds of formula Ib

wherein W and R R to R ^ are as defined for formula I forming part of the invention.

The compounds of formula (Ia) can be prepared by methods known per se, as described in the references cited above, and in the following:

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

f) Chattelain M. and Cabrier P., Bulletin de la Société Chi. tni q ue de France, 1 4 (1 947), 639-642

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

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

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

(j) Simig G., Lemper K. and Tamas J., Tetrahedron, 29 (22), 3571-3578 (1973);

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

l) Muraoka M., Journal of the Chemical Society, Perkin Transactions I, (1990), 3003-3007, or one of the methods A, B, C or D described below.

Compounds of formula (Ib) may be obtained as described by Bohme, Martin and Strahl in Archives der Pharmazie, 313, 10-15 (1980) (ref. D)), or in some of the processes described below.

Method A

Process for the preparation of compounds of the formula I

The preparation of the compounds of the formula I by S-alkylation of the 2-thiohydantoin of the formula II is carried out according to the equation.

(Π) bases

R ₃ x a bromine solvent or iodine atom or sulfa

And in *

wherein X represents a chlorine atom, an atomic group or an alkylsulfonyloxy group or an arylsulfonyloxy group, the alkyl and aryl radicals of said groups having the meanings given above for R1 and R1. ^An alkali metal such as potassium tert-butoxide, an alkali metal or alkaline earth metal hydroxide, an alkali metal carbonate or a tertiary amine may be used as the base. As the solvent, ethers, cyclic ethers, alkyl esters, acetonitrile, alcohols containing 1 to 3 carbon atoms or aromatic solvents such as tetrahydrofuran at -5 to 80 ° C can be used.

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

The 2-thiohydantoins of formula (II) may be obtained by methods described in the literature, for example in the following references:

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

(n) Eberly 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. and Warring W. S., Journal of the Chemical Society (1950), 354-365,

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

i) Koltai E., Nyitrai J., Lempert K. and Burics L., Chemische Berichte, 104, 290-300 (1971), or alternatively one of methods E or F described below, which form part of the invention.

Method B

Preparation of compounds of formula Ic

The preparation of 2-methylthio-2-imidazolin-5-one of formula Ic by cyclization of iminodithiocarbonates of formula V is carried out according to the following reaction scheme

Rj. NH ₂

R, o ₂ H ^{+ CS 1 + 2 CH 2 I} base

(b) / SCH ₃ 'S CH,

R4-- (B) n NH ₂ (TV)

CO, H

R = SCH;

S CH, _from C 1 H - (B) n R,

WHAT

R, ^c ) R 1 = ch, fc = C ³ sch ₃

C-NH- (B) n-R.

O (Ic)

N SCH ₃ N.

^x (B) nR

WHAT

2

a) The iminodithiocarbonates of the formula III can be prepared under 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, according to the following reaction ^R 2 \ NH ₂

R ₂ as H ^{+ CS3 + 2} ™ ³ 'base (in)

b) Compounds of formula V are obtained by condensation of compounds of formula III with amines or hydrazines of formula IV. In order to carry out this condensation, the acid of the formula III must be activated in the form of an acid chloride, in the form of dicyclohexylisourea using dicyclohexylcarbodiimide or in the form of imidazolide using carbonyldiimidazole. This condensation is carried out under conditions customary for this type of reaction.

c) The cyclization of the compounds of formula V is carried out simply by heating in the aromatic solvent at reflux temperature. In particular, xylene, chlorobenzene or dichlorobenzene may be used as the solvent.

Method C

Derivatization of compounds of formulas Ib 'and Id'

3

Method C1

Preparation of Compounds of Formula Ib by N-Derivatization of Compounds of Formula Ib

Compounds of formula Ib (compounds Ib in which R 1 is hydrogen) may be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulfamoylated according to the following equation

N.

SR basis

R <X

Ib 'solvent

wherein R ^ is alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl, as defined above, X is halogen, sulfate or optionally substituted phenoxy or an alkylsulfonyloxy group or an arylsulfonyloxy group or an R 4 O group when R 4 represents an acyl group.

As the base, alkali metal hydrides, alkoxides or a tertiary amine may be used. The reaction may be carried out at a temperature of -30 to 50 ° C. As the solvent, for example, ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide or aromatic solvents can be used.

Carbamoylation of compounds of formula Ib 'may be accomplished by reaction with isocyanates or isothiocyanates according to the equation:

I

4

This reaction is carried out under the conditions described above, but the base can be used in catalytic amounts vi.

Method C2

Preparation of Compounds of Formula Id

Compounds of formula Id (compounds of formula Id in which H is hydrogen) can be alkylated at the 4-position according to the following equation

wherein X represents a chlorine atom, a bromine atom or an iodine atom. As the base, an alkoxide, metal hydride or amide may be used. The reaction may be carried out at a temperature of -30 to 80 ° C. Ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide or aromatic solvents may be used as the solvent.

5

Method D

Preparation of S-oxidized 2-imidazoline-5-thione derivatives

Compounds of formula I wherein W is S = O are obtained by oxidation of 2-imidazoline-5-thiones according to the equation:

Peroxides, especially peroxyacids, can be used as oxidizing agents. This oxidizing agent must be used in a stoichiometric amount. The oxidation is carried out in chloroform or methylene chloride at a temperature of -20 to 20 ° C.

Method E

Preparation of the dithiohydantoin VI

The dithiohydantoins of the formula VI can be obtained by trapping the alpha-anion of an isothiocyanate with isothiocyanates which cannot form anions according to the equation:

R 1 -CH-N = C = S r ₄ -n = c = s

6

At least one of R 6 or R 6 must be an electron-sensing group (aryl, substituted aryl, alkoxycarbonyl, and the like). The isothiocyanate of the formula must not be capable of forming an anion; In particular, arylisothiocyanates may be used in this reaction.

As the base, potassium tert-butoxide, lithium or natriumbis (trimethylsilyl) amide or alkali metal hydrides can be used.

Ethers or cyclic ethers can be used as the solvent. The reaction is carried out at a temperature below -60 ° C. The anion must be captured when it is formed. To achieve this, both isothiocyanates are added to the base in solution at a temperature below -60 ° C.

Method F

Preparation of the 2-thiohydantoin VII

The preparation of 2-thiohydantoin of formula VII from isothiocyanates derived from amino acids of formula VIII is carried out according to the following equation ^R2

R-C-S ^ NzxC

CO ₂ R

R ₄ - (B) n ΝΉ,

This cyclization can be done in two ways:

thermally: in this case the mixture of reactants is heated to a temperature of 110 to 180 ° C in an aromatic solvent such as toluene, xylene or chlorobenzenes;

- in basic medium: cyclization is carried out in the presence of one equivalent of a base such as an alkali metal alkoxide, an alkali metal hydroxide or a tertiary amine. Under these conditions, the cyclization is carried out at a temperature of -10 to 80 ° C. As the solvent, ethers, cyclic ethers, alcohols, esters, dimethylformamide, dimethylsulfoxide and the like can be used.

Said isothiocyanates may be prepared according to any of the methods described in Sulfur Reports, Vol. 8 (5), pp. 327-375 (1989).

Method G

Preparation of compounds of formula I in a single step

During cyclization of the 2-thiohydantoin according to Method F, the thiohydantoin, when cyclized in a basic medium, after completion of the reaction in the thiolate form and may be reacted directly with an alkyl halide or alkyl sulfate R ^ X or a compound R ^ X, which X represents an alkylsulfonyloxy group or an arylsulfonyloxy group to form a compound of formula I. Methods A and F are thus combined together and the formation of a compound of formula I proceeds according to the following reaction scheme.

R, —C — N = C = S i co ₂ r

BM ⁺

R ₄ - (B) n NH ₂ ->

r ₃ x

Method H i

Preparation of compounds of formula Ie in which (D) is a sulfur atom:

T

The following compounds can be obtained by reaction of sulfuryl chloride:

R @ 1 SC @ 1 with an imidazolinone of formula IX;

the following equation

LX

SR '+ R ₄ SC1 base.

solvents

The reaction is carried out at -20 to 30 ° C in the presence of one molar equivalent of the base. As the base, alkali metal hydrides, alkali metal alkoxides or tertiary arine can be used. Polar solvents such as ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, or aromatic solvents may be used as the solvent. The imidazolinones of formula (IX) may be prepared by procedures analogous to Method A.

Compounds which are advantageous because of their superior, fungicidal activity and / or ease of synthesis include:

(1) compounds of formula (1b);

(2) compounds of formula (I), in particular of formula (1b), wherein R R represents a hydrogen atom;

3) compounds in which R ₁ and R ₂ are different from hydrogen,

- 19 4) compounds in which they are alkyl having 1 to 3 carbon atoms,

5) compounds in which it represents a phenyl ring, which is optionally substituted by R 6,

6) compounds in which they are alkyl having 1 to 3 carbon atoms,

7) compounds wherein R 1 is a phenyl group optionally substituted by R 1, and

8) compounds in which R 1 represents a methyl group.

In the following, the invention will be further elucidated by means of specific embodiments of the invention, which are illustrative only and are not intended to limit the scope of the invention, which is clearly defined by the terms of the claims.

DETAILED DESCRIPTION OF THE INVENTION

These examples provide examples of the compounds of the invention and examples of their preparation, and also demonstrate the antifungal activity of these compounds. The chemical structures of all products are verified by at least one of the spectroscopic techniques, including proton nuclear magnetic resonance spectroscopy, C-nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy. The following abbreviations are used in the tables below: m.p. = melting point, Ph = phenyl residue, Me = methyl residue, Et = ethyl residue, Pr = propyl residue, Bu = butyl residue and Pyr = pyridyl residue.

Example 1

Preparation of compound no. 34 method Λ

0.9 g (3 mmol) of 3-benzyl-5-methyl-5-phenyl-2-thiohydantoin is dissolved in 30 ml of anhydrous tetrahydrofuran. The solution was cooled to 0 DEG C. and then potassium tert-butoxide (0.34 g, 3 mmol) was added. The mixture is then allowed to react for 10 minutes at 0 ° C and methyl iodide is added dropwise at this temperature: precipitation of potassium iodide as a precipitate is observed. The reaction mixture is then allowed to warm to ambient temperature. The reaction mixture was diluted with 100 mL of ethyl acetate, and the solution was washed twice with 100 mL of water. The solution is then dried over sodium sulfate and treated with activated charcoal. The solution was then concentrated under reduced pressure to give 1-benzyl-4-methyl-2-methylthio-4-phenyl-2-imidazolin-5-one (Compound 34) as a pale yellow solid.

Yield: 0.6 g, melting point: 68 ° C.

The compounds shown in the following table were prepared in the same manner.

No. R Ka R _t r ₃ W and Physics constant 1 Me Me ph H WITH M.p. = 127’C 3 Me 2-oxo-propyl ph M WITH M.p. = 130 ° C 9 M e Me ph H 0 Mp = 149 ° C 10 Me Me meta-tolyl H 0 M.p. = 124 ° C 11 M e Me p-tolyl H 0 M.p. = 150’C 12 Me et ph H 0 M.p. = 118’C 13 Me Me 4-fluoro Ph H 0 M.p. = 144’C 14 Me allyl ph H 0 M.p. = 92 ° C 15 Me Me ortho-tolyl H 0 M.p. = 92 ° C 16 Me Me 3-chloro Ph H 0 M.p. = 120 ° C 17 Me isopropyl ph H 0 M.p. = 95 ° C 18 Me Me 4-chloro Ph H 0 Mp = 149 ° C 19 Me Me tert-butyl H 0 = 73 ° C 20 Me Me 2-chloro Ph H 0 Mp = 134 ° C 21 M e Me - (CH _{z) 5} - 0 n ’° = 1.551 22 Me Me ph Me 0 M.p. = 124’C 23 Me Me ph acetyl 0 M.p. = 132’C 24 Me Me 4-methoxyPh H 0 M.p. = 138’C 25 Me n-propyl ph H 0 M.p. = 90C 40 Me Me 2-methoxyPh H 0 M.p. = 110 ° C 4 1 Me Me acetyl H 0 M.p. = 55 ° C

No. r ₂ R ₃ R. r ₅ W and Physics constant 4 3 mg Me 4-NO ₂ -Ph H 0 Mp = 133 ° C 4 4 M e Me 2-pyridyl H WITH M. p. Melting point = 114 DEG 45 Me Me 2-pyridyl II 0 M.p. = 147 ° C 4 6 M e M e 3-pyridyl H 0 M.p. = 140 ° C 4 7 M e Me 3-pyridyl H WITH Mp = 176 ° C 54 Me MeS 2,6-Me ₂ Ph H with M.p. = 146 ° C 7 3 Me MeS 2-thia- oxadiazolyl Me 0 M.p. = 116’C 75 Me CHF ₂ S ph H 0 M.p. = 80 ° C 80 Me MeS 3-pyridylCH = - 0 M. p. = 92 ° C 81 Me MeS 2-pyridyl CH = - 0 Mp = 106 ° C 82 Me MeS 4-Me-SO ₂ -Ph H 0 Mp = 130 ° C

No. r ₂ r ₃ R n ^R s w and Physics constant 26 Me Me ph 0 - with Mp = 123 ° C 27 ph Me ph 0 - with M.p. = 120 ° C 28 Me Me Me 0 - with M.p. = 85 ° C 29 ph Me Me 0 - x M.p. = 144 ° C

No. R ₂ ra n r ₅ W Fyz.konstantí 30 M e Me P h 0 - 0 M. p. = 7 0 ’C 31 Me Me Me 0 - 0 M.p. = 58’C 32 ph Me Me 0 - 0 M.p. = 170C 33 H Me ph 0 - 0 M.p. = 250’C 34 Me Me ph 1 H 0 M.p. = 68 ° C 35 Me Me 2-thienyl 1 H 0 M.p. = 76’C 36 Me Me Me 1 Me 0 Πο ° = 1.55 3 37 Me Me 2-furyl 1 H 0 honey-like consistency · 38 Me Me 3-pyridyl 0 - 0 honey-like consistency 50 P h MeS Me 0 H with M.p. = 14 4 ’C. 52 Me MeS ph 1 (CH) E 7 0 honey-like consistency 57 Me MeS 2-MePh 0 - 0 honey-like consistency

The same were prepared also:

- (3-pyridyl) -4-methyl-1- (N-phenylamino) -2-methylthio-2-imidazolin-5-one (Compound No. 51, mp: 156 ° C), and

4-Phenyl-4-methyl-1- (benzyloxy) -2-methylthio-2-imidazolin-5-one (Compound No. 56, honey-like consistency).

Example 2

Preparation of Compound # 7 in Method B

Step a)

N- (bis (methylthio) methylene) -2-phenylglycine (a compound of formula III wherein R 1 is phenyl and R 1 is hydrogen)

100 g (0.66 mol) of phenylglycine were dissolved at 335C in 335 g of 22% aqueous potassium hydroxide solution (1.3 mol).

55.3 g of carbon disulfide are then added with vigorous stirring, the precipitate is formed and the mixture turns orange. The mixture is allowed to react for 3 hours at room temperature, then 103 g (0.73 mol) of methyl iodide are added, maintaining the reaction mixture temperature below 30 ° C. The reaction mixture was allowed to react for 30 minutes, then 74 g (0.66 mol) of a 50% aqueous potassium hydroxide solution was added. The mixture is left to react for 30 minutes, then 103 g of methyl iodide is added and the mixture is left to react for 1 hour. The reaction mixture is then diluted with 300 ml of water and acidified with 1N hydrochloric acid to pH = 4. The product is extracted with 500 ml of ethyl acetate.

The solution was dried over magnesium sulfate and concentrated under reduced pressure to give N- (bis (methylthio) methylene) -2-phenylglycine as a yellow solid.

Yield: 49.5 g (31%), m.p. 112 ° C.

Step b);

i;

and

2 '- (Methylchlorophenyl) - N - {bis (methylthio) methylene) -2-phenylglycyl / hydrazide (compound of formula V in which R 1 represents a phenyl group is a hydrogen atom, R 1 represents a methachlorophenyl group, n is equal to 1 and B is Nil)

To a solution of 2.95 g (16.4 mmol) of N- (bis (methylthio) methylene) 2-phenylglycine in methylene chloride (40 ml) was added 3.38 g (16.4 mmol) of dicyclohexylcarbodiimide and the mixture was allowed to react at ambient temperature. temperature for 30 minutes. 2.34 g (16.4 mmol) of methachlorophenylhydrazine are then added. The mixture is then heated to 30 ° C for 30 minutes. The insoluble matter is filtered off.

The filtrate is washed twice with 30 ml of water. The solution is then concentrated to give a honey-like product which is purified by chromatography on silica gel. Purification yielded 2 '- (methachlorophenyl) - N - (bis (methylthio) methylene) -2-phenylglycyl] hydrazide as a pinkish powder.

Yield: 2.5 g, melting point: 146 ° C.

Step c)

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

1.92 g (5 mmol) of 2 (methachlorophenyl) - N - (bis (methylthio) methylene) -2-phenylglycyl] hydrazide are dissolved in 30 ml of xylene.

The reaction mixture is then heated to reflux for 4 hours. The reaction mixture is then concentrated under reduced pressure. The honey product obtained is triturated with 10 ml of ether and crystallized. The precipitated crystalline precipitate is filtered off and dried in a desiccator under vacuum. Compound 7 is obtained as a yellow powder.

Yield: 56%, m.p. 196. ° C.

The compounds listed in the following table are prepared in an analogous manner.

and Physics

No. R ₂ R ₃ R <Rj w constant

4 H Me 2-chloro Ph H 0 M.p. = 130 ° C 5 H Me ph H 0 M.p. = 190 ° C 6 H Me 4-chloro Ph H 0 Mp = 162 ° C 7 H M e 3-chloro Ph H -.0 Mp = 196 ° C 8 H Me meta-tolyl H 0 M.p. = 182 ° C 59 H MeS 2,4- (CH _{3) 2} Ph H 0 M.p. = 64 ° C 61 H MeS 2,5 (CH _{3) 2} Ph H 0 Mp = 162 ° C 63 H MeS 2-EtPh H 0 M.p. = 126’C 69 H MeS 2,5- (Cl) ₂ Ph H 0 M.p. = 144’C 71 H MeS 3,5- (Cl) ₂ Ph H 0 M.p. = 146’C

The same was prepared for 4-phenyl-1- (N-phenylamino) -2-methylthio-2-imidazolin-5-one (Compound No. 120).

Example 3

Preparation of 4-methyl-1- (N-methyl-N-phenylamino) -2-methylthio-4-phenyl-27

Of 2-imidazolin-5-one (Compound No. 22) by alkylation (methylation) of m.p.

H by Cl j i

I.

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), cooled to 0 ° C, the following is added:

0.4 g (3.5 mmol) of potassium tert-butoxide. The mixture was then dipped;

0.5 g (3.5 mmol) of methyl iodide was added thereto and the mixture was allowed to react at room temperature for 30 minutes. The reaction mixture is then poured into

100 ml of water and the product was extracted with 100 ml of diethyl ether. The ether solution was dried over magnesium sulfate and then concentrated. After trituration in 10 ml of diisopropyl ether, the product crystallizes.

Filter and dry under vacuum. In this way, Compound No. 22 is obtained as a pale yellow powder.

Yield: 0.73 g (70%), m.p. 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) by Method C1

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), cooled to at 0 ° C, 0.4 g (3.5 mmol) of potassium tert-butoxide is added. The mixture is allowed to react at 0 ° C for 30 minutes. Then, 0.25 g (3.5 mmol) of acetyl chloride is added to the mixture and the mixture is allowed to react at room temperature for 30 minutes. The reaction mixture is then poured into 100 ml of water and the product is extracted with 100 ml of diethyl ether. The ether solution was then washed with water until neutral.

The solution was dried over magnesium sulfate and then concentrated. The resulting honey-like consistency is purified by chromatography

i iiiisawM

í., ';.' · '·' - '. · .. Λ

- 28 silica gel. The purified product is then left to crystallize from diisopropyl ether. Compound No. 23 is thus obtained in the form of a white powder.

Yield: 0.25 g, m.p. 132 ° C.

In the same way, the compounds which are also listed in the table below are prepared.

No.

R ₂ * 3

Physical R ₅ W constant

23 Me Me ph acetyl 0 M.p. = 132 ° C 39 Me Me ph formyl 0 ..... medoviteí consistency · 4 2 Me Me ph tBuOCO 0 honey-like consistency

Example 5 f Preparation of 4-ethyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (Compound No. 48) by Method C2

To a solution of 1.5 g (5.05 mmol) of 2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound 5) in 50 mL of anhydrous tetrahydrofuran was added 0.55 g of tert. of potassium butoxide. The mixture was allowed to react at room temperature for 30 minutes, then 0.8 g (5.05 mmol) of ethyl iodide was added. The reaction mixture is then allowed to react at room temperature for one hour.

The mixture was diluted with 150 mL of ethyl acetate. The solution was washed with water and concentrated under reduced pressure. The product was purified by silica gel column chromatography (Merck silica gel 60H; elution system consisting of 25% ethyl acetate and 75% heptane). In this way, compound no. 48 in the form of a beige powder. Yield: 0.65 g, melting point: 147 ° C.

Compound No. 49 as well as the other compounds listed in the following table were prepared in the same manner.

and Physics

No. K ₂ ^R 3 ^R 5 ^w constant

48 E t Me ph H 0 M.p. = 147 ° C 49 iso-Pr Me ph H 0 M.p. = 135 ° C 60 Me MeS 2,4- (Me) _from Ph H 0 honeycomb consistency 62 Me MeS 2,5- (Me) _from Ph H 0 Mp = 160 ° C 64 Me MeS 2-EtPh H 0 honey-like consistency 65 Me MeS 2,4- (Cl) _of Ph H 0 66 Me MeS 1-naphthyl H 0th Mp = 174 ° C 70 Me MeS 2,5- (Cl) _of Ph H 0 M.p. = 180 ° C 72 Me MeS 3,5- (Cl) _of Ph H 0 M.p. = 200 ° C 74 chf ₂ MeS ph H 0 M.p. = 124 ° C 79 Me MeS 2-CF ₃ -Ph H 0 M.p. = 91 ^ 0

4-Methyl-2-methylthio-4- (4-fluorophenyl) -1-phenylamino-2-imidazolin-5-one (Compound No. 60) was also prepared.

Example 6

Preparation of Compound # 2 in Method D

1.7 g (5.2 mmol) of 4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazoline-5-thione (compound 1) are dissolved in 20 ml of chloroform. The solution was cooled to -10 ° C and a solution of 1.35 g (5.5 mmol) of metachloroperbenzoic acid and 30 ml of chloroform was added over 10 minutes. After completion of the addition, the reaction mixture is allowed to warm to ambient temperature. The reaction mixture was then washed with saturated aqueous sodium bicarbonate solution and then with distilled water. The organic phase is treated with activated carbon and then concentrated. The honey-like product obtained is taken up in ether (20 ml): the product is dissolved and then precipitated as a beige solid. The precipitate was filtered off and the product was dried under reduced pressure. In this way compound 2 is obtained in the form of a beige powder. Yield: 0.4 g (25%), m.p. 150 ° C.

No. r ₂ ro R < ri w, and Physics constant 2 Me Me ph H s = o M.p. = 150 ° C

Example 7

Preparation of 3,5-diphenyl-5-methyldithiohydantoin by Method E

Dissolve 15.1 g (122 mol) of potassium tert-butoxide in 200 ml of tetrahydrofuran placed in a 500 ml three-necked round-bottomed flask under an argon atmosphere. The resulting solution was cooled to -70 ° C. A solution containing 20 g (122 mmol) of alphamethylbenzyl isothiocyanate, 16.55 g (122 mmol) of phenyl isothiocyanate and 50 ml of tetrahydrofuran is then added dropwise while maintaining the reaction temperature below -60 ° C. Upon completion of the addition, the reaction mixture is maintained at -70 ° C for 30 minutes, then allowed to warm to ambient temperature. The reaction mixture is then poured into 500 ml of water. The resulting mixture was acidified to pH = 1 by addition of 1N hydrochloric acid. The product was extracted with ethyl acetate (2 extractions, each with 150 ml of solvent). The resulting solution was dried over magnesium sulfate. The solution is then concentrated under reduced pressure and the product is crystallized from 50 ml of ether. The precipitate formed is filtered off. There was thus obtained 3,5-diphenyl-5-methyldithiohydantoin as a yellow powder.

Yield: 21 g (58%), m.p. 157 ° C.

Example 8

Preparation of 3,5-diphenyl-5-methyl-2-thiohydantoin by Method F

4.7 g (20 mmol) of ethyl 2-isothiocyanato-2-phenylpropionate are dissolved in 40 ml of xylene. Phenylhydrazine (2.16 g, 20 mmol) was added and the mixture was refluxed for 4 hours. The mixture was then cooled to ambient temperature, whereupon a beige precipitate formed. The precipitate was filtered off, washed with 5 ml of diisopropyl ether and dried under vacuum. In this way 3,5-diphenyl-5-methyl-2-thiohydantoin is obtained in the form of a beige powder.

Yield: 4.6 g (77%), melting point: 164 ° C.

Example 9

Preparation of 5-methyl-5-phenyl-3- (2-pyridylamino) -2-thiohydantoin a

Method F g (9 mmol) of methyl 2-isothiocyanato-2-phenylpropionate was dissolved in 30 ml of tetrahydrofuran. A solution containing 0.99 g of 2-hydrazinopyridine and 10 ml of tetrahydrofuran was added to the obtained solution: the temperature of the reaction mixture rose from 20 to 30 ° C and a precipitate formed. The reaction mixture is allowed to react at 30 ° C for 30 minutes and then cooled to 5 ° C. A solution containing 1 g of potassium tert-butoxide and 10 ml of tetrahydrofuran was added to the mixture: the mixture obtained a violet coloration. The mixture was then allowed to warm to room temperature and allowed to react for 2 hours. The reaction is reduced

It is then poured into 150 ml of water and neutralized with acetic acid. The product was extracted with 150 mL of ethyl acetate. The solution obtained is washed with water, dried over magnesium sulphate and then treated with activated carbon. The solution is concentrated and the product is crystallized from 20 ml of diethyl ether, then filtered off and dried under vacuum. There was thus obtained 5-methyl-5-phenyl-3- (2-pyridylamino) -2-thiohydantoin as a pale yellow solid.

Yield: 1.6 g (60%), m.p. 80 ° C.

In this way, the compounds of the general formula (VII) listed in the following table, which are intermediates for the preparation of the compounds of the general formula (Ia), are numbered from the number 1001.

<ΎΠ) r = methyl and ”phenyl

1 _ - c. n 3 R. Yield temperature melting 1001 1 N H ph 66% 164 ° C 1002 1 NH meta-tolyl 62 174 ’C 1003 1 ch ₂ ph 46% 125'C 1004 1 NH p-tolyl 13% 162 ° C 1005 1 ch ₂ 2-thienyl 49.5% 134 ’C 1006 1 NH 4-fluoro · Ph 30% .. 162 ° C 1007 1 NH ortho-tolyl 3 8% 162 ° C 1008 0 - isopropyl 60.5% 146 ° C 1009 1 NH 3-chloro · Ph 32% 78 ° C 1010 1 NH tert-butyl 18% 120 ° C 1011 1 NH 4-chloro Ph 24% 196 ° C 1012 1 NH 2-chloro> Ph 6? ’% 172 ° C 1013 0 - piperidino 32% 206'C 1014 1 NH 4-methoxyPh 27% 146 ° C 1015 1 NH 2-methoxyPh 29% 214 ° C 1016 1 ch ₂ 2-furyl 39% 105 ° C 1017 1 NH acetyl 42% 200 ° C 1018 1 NH 4-NO ₂ -Ph 41,% 234 ° C 1019 1 NH 2-pyridyl 60% 80 ° C 1020 1 NH 3-pyridyl 17%

T

Example 10

Preparation of Compound # 9 in Method G

11.1 g (50 mmol) of methyl 2-isothiocyanato-2-phenylpropionate are dissolved in 150 ml of anhydrous tetrahydrofuran. The solution containing 5.4 g (50 mmol) of phenylhydrazine and 50 ml of anhydrous tetrahydrofuran was then added gradually over 10 minutes while the temperature of the reaction mixture rose to 35 ° C. Upon completion of the addition, the reaction mixture was allowed to react at 30 ° C for 30 minutes and then cooled to -5 ° C. A solution containing 5.6 g (50 mmol) of potassium tert-butoxide and 50 ml of anhydrous tetrahydrofuran is added at this temperature, whereupon the reaction mixture turns violet and a precipitate is formed. The mixture is then allowed to react at 0 ° C for 30 minutes and 8.5 g (60 mmol) of methyl iodide are added. The reaction mixture is then allowed to react at ambient temperature for one hour. The mixture was then diluted with 200 mL of ethyl acetate. The mixture is washed twice with 150 ml of water. The solution is dried over magnesium sulphate and treated with activated charcoal. The solution is then concentrated to give a purple brownish honey-like product which is crystallized from 50 ml of ether. The crystalline product is washed and then dried under vacuum. A second crop of product was isolated after concentration of the mother liquor and removal of the honey product thus obtained with 50 ml of diisopropyl ether. There was thus obtained 4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound 9) as a beige powder.

Yield: 12 g (77%), m.p. 149 ° C.

The compounds listed in the following table are also prepared as described above.

No. «3 B Melting point 58 Me MeS NH 2,3- (Me) ₂ Ph 116 ’C 67 Me MeS (CH ₂ ) ₂ ph honey-like consistency 76 - Me MeS ch ₂ 3-pyridyl 67 “C 77 - Me MeS ch ₂ 2-pyridyl rnedovi ta kons.istence 70 - Me MeS N Ph = 95 ° C 83 4-Me Me MeS NH ph 179 ° C 84 - Me MeS NH 3-Me-2-Pyr 148 ° C 85 4-C1 Me MeS NH ph 173 ° C 86 3,4- (MeO) ₂ Me MeS NH ph \ 65 ° C 87 3,4- (MeO) ₂ Me MeS NH 2-Me-Ph d. 88 4-Me Me MeS NH 2-Me-Ph ' 52 ° C 89 4-Ph Me | MeS NH ph 146 ° C 90 4-C1 Me MeS NH 3-Me-2-Pyr 133 ° C 91 4-C1 Me MeS NH 2-pyridyl 172 ’C 92 _T R = PhCH ₂ Me MeS NH ph 166 ° C 93 4-Ph Me MeS NH / 2-Me-Ph 130 ° C 94 4-F Me MeS NH 2-Me-Ph 120 ° C 96 4-C1 Me MeS NH 2-Cl-Ph 145 ° C 97 - (CH ₂ ) ₃ MeS NH ph 158 ’C 9 8 - (CH ₂ ) ₂ MeS NH ph 85 DEG C. 99 4-C1 H MeS NH 4-Cl-Ph 163 ° C 100 4-C1 Me MeS NH 4-Cl-Ph 172 ° C

No. R & apos r ₂ ra B ra melting point 101 4-C1 Me MeS NH 4-F-Ph 170 ° C 102 4-C1 Me MeS NH 3-Cl-Ph 146'C 103 4-C1 Me MeS NH 4-Me-Ph 178 ° C 104 - (CH ₂ ) ₃ MeS NH 2-Cl-Ph 168'C 105 4-C1 Me MeS NH 2-Me-Ph 124 ° C 106 4-Cl Me MeS N H 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-F ₂ -Ph 14l'C 110 4-Me Me MeS NH 4-Cl-Ph 168'C 111 4 - Me Me MeS NH 2-Cl-Ph 168'C 112 - (CH ₂ ) ₃ MeS NH 4-Cl-Ph 191 ° C 113 - (CH ₂ ) ₃ MeS NH 2-Me-Ph 174 ° C 114 4-Me Me MeS NH 3-Cl-F H 184'C 115 4-F Me MeS NH 3-Cl-Ph 124'C 116 4-Me Me MeS NH 4-F-Ph 136'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 122 - Me MeS NH 2,4- (Me) _z -Ph 63'C 123 - Me MeS NH 3-Cl-2-Pyr 127'C 12 4 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

· Μ. \

- 37 Example 1 1

Preparation of 4-phenyl-4-methyl-1- (phenylthio) -2-methylthio-2-imidazolin-5-one (Compound No.95)

0.6 g (2.7 mmol of 2-methylthio-4-methyl-4-phenyl-2-imidazolin-5-one in solution in 50 ml of anhydrous tetrahydrofuran) is introduced into a 100 ml round-bottomed flask under an inert atmosphere. magnetic stir bar, and cooled to 0 ° C in an ice-acetone bath. then, 0.30 g (1 molar equivalent) of potassium tert-butoxide and the mixture was stirred for 10 minutes at 0 ° ^C.? the mixture was then A solution containing 0.40 g of phenylsulfenyl chloride and 10 ml of anhydrous tetrahydrofuran was added and the reaction mixture was allowed to warm to ambient temperature for one hour and then treated with 100 ml of water and extracted with 100 ml of ethyl acetate. The organic phase is washed four times with water and then dried over sodium sulphate.

The organic phase is concentrated under vacuum and the yellow product of ice-like consistency obtained is crystallized from isopropyl ether after chromatography on silica gel.

Yield: 68%, melting point: 112 ° C.

Example 12

In vitro test /

The activity of the compounds of the invention has been studied in the following fungi which cause diseases of cereals and other plants:

Fusarium oxysporum f.sp.melonis

Rhizoctonia solani AG4

Kelminthosporium gramineum,

Pseudocercosporella herpotrichoides,

Alternaria alternata,

Septoria nodorum,

ΛΧΛϋ ·

- 38 Fusarium roseum Pythium rostratum - Pythium vexans.

Each test was performed as follows: Potato substrate, glucose and gelatin (PDA nutrient broth) were sterilized in an autoclave at 120 ° C in a supercooled state in a series of petri dishes (100 ml of nutrient media in each petri dish). ). When filling Petri dishes, an acetone solution of the active ingredient is injected into the subcooled culture medium in an amount providing the desired final active ingredient concentration.

The control bodies consist of petri dishes of the same type, which were filled with the same amount of the above nutrient medium, but to which no active substances were added. After 24 hours, each dish is inoculated with a fragment of soil mycelium resulting from the initial culture of the corresponding fungus. The petri dishes are then held for 5 days at 20 ° C, whereupon the growth of the fungi in the petri dishes containing the active substances is compared with the growth of the same fungus in the petri dishes serving as the control subject, i.e. in control plates containing no active substances?

For each test compound, the degree of inhibition of fungal growth was determined at a concentration of 20 ppm.

The following results were obtained with this test:

Good activity, corresponding to a degree of inhibition of fungal growth of between 80 and 100%, was found in:

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

- compounds

- compounds

- compounds

- compounds des, for Fusarium oxysporum and Fusarium roseum,

11, 16, 22 and 26 for Alternaria alternata,

11, 16 and 26 for Rhizoctonia solani, and 26 for Pseudocercosporella herpotricho 39 - compounds 11, 16 and 26 for Septoria nodorum, and

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

Example 13

In vivo test for vine headstock (Plasmopara viticola)

By finely grinding, an aqueous suspension of the test compound is prepared having the following composition:

- active substance: 60 mg,

- Tween 80 surfactant (polyoxyethylene sorbitan oleate) diluted with water to a concentration of 10%:

0,3 ml,

- volume to 60 ml with water.

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

Vine cuttings (Vitis vinifera), a variety of Chardonnay, are planted in a pot. When the vine plants are two months old (stage 8-10 leaf, height 10-15 cm), they are sprayed with the above aqueous suspension. The vine plants serving as control subjects are sprayed with solutions containing no active substance. After drying the plants for 24 hours, each plant is infected by spraying an aqueous suspension of Plasmopara viticola spores obtained from a 4-5 day culture suspended in a quantity of seed. 3 giving a concentration of 100,000 units / cm. The infected plants are then incubated for two days at a temperature of about 18 ° C in an atmosphere saturated with humidity and then for five days at a temperature of about 20-22 ° C and a relative humidity of 90-100%. Assessment of plant condition is performed seven days after infection by comparison with control plants.

Under these conditions, good protection (at least 75%) or complete protection was found at a concentration of 1 g / l for 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 50, 60, 62, 64, 68, 73, 75, 76, 83 to 85, 80 to 91, 93 to 98, 101 to 108.

Example 14

In vivo test for Puccinia recondita wheat slice

An aqueous suspension of the test compound having the following composition is prepared by fine grinding:

- active substance: 60 mg,

- Tween 80 surfactant (polyoxyethylenated sorbitan derivative oleate) diluted with water to a concentration of 10%: 0,3 ml,

- volume to 60 ml with water.

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

Wheat sown in pots in a soil substrate consisting of 50% peat and 50% pozzolan is sprayed with the above aqueous suspension when it has reached a height of about 10 cm.

After 24 hours, spray an aqueous spore suspension 3 (100,000 spores / cm) on wheat. This suspension was obtained from infected plants. The wheat is then stored for 24 hours in an incubation cell in which a temperature of about 20 ° C and a relative humidity of 100% is maintained, after which the wheat is maintained for 7-14 days at a relative humidity of 60%. /

Evaluation of the plant condition is performed between 8 and 15 days after infection by comparison with the condition of untreated control plants.

Under these conditions, good protection (at least 75%) or complete protection was found at a concentration of 1 g / l for the following compounds: 2, 9, 10, 15, 18, 20-22 and 39, 55, 57, 64, 68, 75 , up to 85, 88 to 90, 93, 94 and 98.

Example 15

- 41 In vivo test for Phytophthora infestans

By finely grinding, an aqueous suspension of the test compound is prepared having the following composition:

- active substance: 60 mg

- Tween 80 surfactant (polyoxyethylenated sorbitan oleate) diluted to 10% with water:

0,3 ml,

- make up to 60 ml with water.

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

The tomato plants used in this test are of the Marmande variety and are planted in pots. When these plants are one month old (5 to 6 leaf stage, 12 to 15 cm high), they are sprayed with the above aqueous suspension containing different concentrations of the test compound. After 24 hours, each plant is infected by spraying with 3 aqueous spore suspension (30,000 spores / cm) of Phytophthora infestans.

After this infection, the tomato plants are incubated for 7 days at a temperature of about 20 ° C in a humidified atmosphere. Seven days after infection, the results obtained for plants treated with test active substances are compared with those obtained for plants used as control subjects. Under these conditions, good protection (at least 75%) or complete protection was observed at a concentration of 1 g / l for compounds 2, 9, 15, 30, 39, 45, 55, 68, 75, 84, 85, 90, 94, 98 , 107 and 108.

Clearly demonstrate these results! the good fungicidal properties of the derivative according to the invention for fungal slatted diseases caused by fungi belonging to the most diverse families, such as Phycomycetes, Basidiomycetes, Ascomycetes, Adelomycetes or Fungi Imperfecti, in particular against the headworm of Pestina pestinae, Plasmesthia spp.

In practice, the compounds of the invention are rarely used alone. Most often they form part of the compositions. These compositions, which can be used as fungicidal agents, contain the compound of the invention described above as an active ingredient, and in such a composition it is admixed with an agriculturally acceptable solid or liquid carrier and an agriculturally acceptable surfactant. In particular, conventional inert carriers and conventional surfactants are used. These compositions also form part of the invention.

The compositions may also contain all kinds of other conventional additives such as protective colloids, adhesives, thickeners, thixotropic agents, stabilizing agents and sequestering agents. Usual! the compounds of the invention may be used in combination with any of the usual solid or liquid additives which correspond to conventional formulation techniques.

The compositions of the invention typically comprise 0.05 to about 95% by weight of a compound of the invention (hereinafter referred to as the active ingredient), at least one solid or liquid carrier and optionally at least one surface active agent.

As used herein, the term carrier refers to a natural or synthetic organic or inorganic substance with which the active substance is combined to facilitate its application to the plant or seed or to the soil. This carrier must therefore be generally inert and acceptable for agricultural use, in particular acceptable for the plant to be treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers and the like) or liquid (water, alcohols, especially butanol and the like).

The surfactant may be an emulsifying, dispersing or wetting agent of the ionic or non-ionic type or a mixture of such surfactants. Examples of surfactants which may be mentioned are poly (acrylic acid) salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensation products of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols). , sulfosuccinic acid ester salts, taurine derivatives (especially alkyltaurates), phosphoric acid esters of polyoxyethylenated alcohols or phenol, fatty acid esters and polyols, and derivatives of the above compounds having a sulfate, sulfonate or phosphate functionality. The presence of at least one surface-active agent is usually necessary when the active ingredient and / or the inert carrier are not water-soluble and the carrier medium of the applied composition is water.

Compositions for agricultural use according to the invention may thus contain the active compounds according to the invention within a wide range of from 0.05 to 95% by weight. The surfactant content of these compositions may range from 5 to 40% by weight.

The compositions of the invention are in solid or liquid form.

Powders for dusting (containing up to 100% active ingredient) and granules, in particular granules obtained by extrusion, compression, impregnation of a granular carrier or powder granulation (active ingredient content of these granules for the latter cases), may be mentioned as solid forms of the compositions of the invention. between 0.5 and 80%) as well as tablets or effervescent tablets.

When the compounds of formula I are used in the form of a dusting powder, a composition comprising 50 g of active ingredient and 950 g of talc may be used. A composition comprising 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc may also be used. Said components are mixed together and ground together to form a mixture which can be applied as a dusting agent.

As forms of compositions which are liquid or which form a liquid composition at the time of application, solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or sprayable powders), pastes or gels, may be mentioned.

I

Emulsifiable or soluble concentrates most commonly contain 10 to 80% active ingredient, while ready-to-use solutions or emulsions contain 0.001 to 20% active ingredient.

In addition to the solvent, the emulsifiable concentrates may contain, if desired, 2 to 20% of suitable additives, such as stabilizing agents, surface active agents, penetrating agents, corrosion inhibitors, dyes or the above-mentioned adhesives.

By diluting said concentrates with water, it is possible to obtain emulsions of any desired concentration which are particularly suitable for application to crop plants.

Two examples of emulsifiable concentrates will be given below.

Emulsifiable concentrate

Contents folder (G / l) active substance 400 alkali metal dodecylbenzenesulfonate 24 oxyethylenated nonylpenol containing 10 molecules of ethylene oxide 1 6 cyclohexanone 200 aromatic solvent added to 1 liter

Emulsifiable concentrate

IngredientContent of active ingredient 250 epoxidized vegetable olel 25 mixture of alkylarylsulfonate and polyglycol and fatty alcohol ether 100 dimethylformamide 50 xylene 575 s

'"in

Suspension concentrates, which can also be applied by spraying, are prepared to represent a stable, non-sedimented liquid product, the suspension concentrates usually containing 10 to 75% active ingredient, 0.5 to 15% surfactants · 0.1 up to 10% of thixotropic agents, 0 to 10% of suitable additives such as antifoams, corrosion inhibitors, stabilizing agents, penetrating agents and adhesives, and as a carrier a water or organic liquid in which the active ingredient is only slightly soluble or completely insoluble. Certain organic or inorganic substances may be dissolved in the carrier to prevent settling or freezing of water.

An example of a suspension concentrate will be given below.

Suspension concentrate

Ingredient (g) active ingredient 500 polyethoxylated tristyrylphenyl phosphate 50 polyethoxylated alkylphenol 50 sodium polycarboxylate 20 ethylene glycol 50 organopolysiloxane oil (defoamer) 1 polysaccharide 1.5 water 316.5

Wettable powders (or spray powders, sprayable powders) are usually formulated to contain 20 to 95% active ingredient, in addition to the active ingredient usually also containing a solid carrier, 0 to 30% wetting agent, 3 to 20% dispersing agent, and optionally 0.1 to 10% of at least one stabilizing agent and / or other additives such as penetrating agents, adhesives, antisedimentants, dyes and the like.

In order to obtain sprayable or wetting powders, the active compounds are intimately and homogeneously mixed in suitable mixers.

component Contents (%) active substance 75 a desiccant 1, 50 dispersing agent 8 calcium carbonate (inert filler) 100 Wettable powder 4 component Contents (%) active substance 90 ethoxylated fatty alcohol (wetting agent) 4 ethoxylated phenyl thylphenol (dispersing agent) 6

Wettable powder 5

Component_Content_ (%) Active ingredient 50 mixture of anionic and non-ionic surfactants (de-surfactant) 2,5 Sodium lignosulfonate (dispersant) 5 Kaolin (inert carrier) 42,5

Aqueous dispersions and emulsions, such as compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are also within the scope of the invention. The emulsions may be water-in-oil or oil-in-water emulsions and may have a thick mayonnaise-like consistency.

The compounds of the invention may also be formulated into water-dispersible granules, which are also within the scope of the invention.

These dispersible granules having a density of about 0.3 to 0.6 have a particle size of usually between about 150 and 2000 microns and preferably between 300 and 1500 microns:

The active ingredient content of the granules is usually between about 1 and 90%, preferably between 25 and 90%. The remainder of the granule is essentially comprised of a solid filler and optional surface active ingredients which impart the ability of the granules to disperse in water. These granules may be essentially granules of two basic types, depending on whether the filler used is soluble or insoluble in water. If the filler is water-soluble, it may be an inorganic or preferably organic substance. Excellent results are obtained using urea. In the case of a water-insoluble filler, the filler is preferably an inorganic substance such as kaolin or bentonite. The filler is then preferably accompanied by surfactants (in an amount of 2 to 20% by weight based on the weight of the granule), more than half of which are, for example, at least one substantially anionic dispersant such as an alkali metal or alkaline earth metal polynaphthalenesulfonate; an alkali metal or alkaline earth metal lignosulfonate, and the remainder being nonionic or anionic wetting agents such as an alkali metal or alkaline earth metal alkyl naphthalenesulfonate.

In addition, other additives, such as antifoams, may be added, although the presence of these substances is not necessary.

The granules of the invention may be prepared by mixing the desired ingredients and subsequently granulating the mixture thus obtained by one of the known granulation techniques (pelletizer, fluid bed, atomizer, extrusion and the like). Typically, the preparation of the granules is completed by grinding and subsequent sieving to obtain granules having a size within the aforementioned required limits.

Preferably, the granules are obtained by extrusion and the preparation of the granules is carried out in the manner described in connection with the two examples of dispersible granules set forth below.

Dispersible granules

90% by weight of active ingredient and 10% urea in bead form are mixed in a blender. This mixture is then ground in a roller mill. The powder obtained is then moistened with approximately 8% by weight of water. The wet powder is then extruded with a perforated roller extruder. the obtained granules are dried and sieved so that only granules between 150 and 2000 microns are retained in situ.

Dispersible granules 2

The following ingredients are mixed in the blender:

active ingredient 75% wetting agent (sodium alkylnaphthalenesulfonate) 2% dispersing agent (sodium polynaphthalenesulfonate) 8% water insoluble inert filler (kaolin) 15%.

The mixture is granulated in a fluidized bed in the presence of water, then dried, crushed and sieved to separate granules between 0.15 and 0.80 mm in size.

These granules may be used alone or in the form of an aqueous solution or dispersion to achieve the desired concentration of active ingredient. These granules may also be used in combination with other active substances, in particular fungicides, the latter being in the form of wettable powders or granules or aqueous suspensions. For compositions which are suitable for storage and transport, these compositions are more preferably contain from 0.5 to 95% by weight of active ingredient.

The invention also encompasses the use of the compounds of the invention for combating fungal plant diseases by preventive or curative treatment of these plants or the environment in which they grow. These compounds are preferably applied at application rates of 0.005 to 5 kg / ha, in particular 0.01 to 1 kg / ha.

Claims (36)

1. Compounds containing an imidazolinone or imidazolinthione group of the formula I (I / c. W A n B is sulfur or oxygen or S = O, oxygen or sulfur, 0 or 1, NR6 or oxygen or sulfur, or CR3-R8 or SO ^ or C = O, R, which are the same or different, represents a hydrogen atom, provided that one of the groups is different from a hydrogen atom, or an alkyl or haloalkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl group 2 to 6 carbon atoms or a dialkylaminoalkyl or cycloalkyl group containing 3 to 7 carbon atoms or an aryl group comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinoline, or methylenedioxyphenyl, each of which may be optionally substituted by 1 Or arylalkyl, aryloxyalkyl, arylthioalkyl or. an arylsulfonylalkyl group in which the aryl and alkyl radicals are as defined above, or R 2 and R ₂ together with the carbon atom to which they are attached may form a carbocyclic or heterocyclic group of 5 to 7 atoms, which groups may be condensed to a phenyl ring optionally substituted with 1 to 3 groups selected from R 6; . R 1 represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkylcarbonyl, alkoxycarbonylalkyl or alkoxycarbonylalkyl group; N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atorne or arylalkyl groups in which the alkyl moiety contains 1 to 6 carbon atoms and the aryl moiety is a phenyl, naphthyl, thienyl, furyl or pyridyl group optionally substituted by 1 to 3 groups selected from of the meaning of R 1,> R. represents a hydrogen atom when n is 1, or an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyoyl or Nalkylcarbonylaminoalkyl group 3 to 6 carbon atoms III N, N-dialkylcarbamoylalkyl of 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or a methylenedioxyphenyl group, each of which may be optionally substituted with 1 to 3 groups selected from R ^, or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group in which the aryl and alkyl radicals are as defined above, or an amino group disubstituted by two the same or different groups selected from the group consisting of alkyl of 1 to 6 carbon atoms, alkoxyalkyl, alkenyl or alkynyl of 3 to 6 carbon atoms. a cycloalkyl group containing 3 to 6 carbon atoms, an arylalkyl group as defined above, a phenyl group or a naphthyl group optionally substituted by 1 to 3 groups selected from R R, or a thienylmethyl or furfuryl group, a pyrrolidine, piperidine, morpholine or piperazine group , optionally substituted alkyl having 1 to 3 carbon atoms, R1 represents a hydrogen atom with the exception of R1 represents a hydrogen atom or an alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl or alkoxyalkyl a group containing from 2 to 6 carbon atoms; or IV a alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl group containing 3 to 6 carbon atoms or a formyl group or a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl group having 3 to 6 carbon atoms or a cycloalkylcarbonyl group or a cycloalkylcarbonyl group or a cycloalkylcarbonyl group, in particular phenylacetyl and phenylpropionyl, arylcarbonyl, especially benzoyl optionally substituted with 1 to 3 groups selected from R R, thienylcarbonyl, furylcarbonyl, pyridylcarbonyl, benzyloxycarbonyl, pyridylcarbonylmethyl, thienylcarbonylmethyl, thiophenylcarbonyl, thienylcarbonyl, thienylcarbonyl, thienylcarbonyl, thienylcarbonyl, thienylcarbonyl; a group, a phenoxycarbonyl group or a (phenylthio) carbonyl group in which the phenyl moiety is pr optionally substituted with 1 to 3 groups selected from R R, (alkylthio) carbonyl, (haloalkylthio) carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl, (furfurylthio) carbonyl, (tetrahydrofurfurylthio) ) carbonyl, (thienylmethylthio) carbonyl, (pyridylmethylthio) carbonyl or arylsulfonyl or carbamoyl, optionally mono- or disubstituted groups selected from the group consisting of alkyl or haloalkyl of 1 to 6 carbon atoms or cycloalkyl, alkenyl or an 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 with 1 to 3 - B 2 z. The I selected from the meaning of R ', ^T,' I'f sulfamoyl diethylcarbamoyl group, a t sulfamyl further optionally mono- or di-substituted with groups selected from the group consisting of F alkyl or haloalkyl radical having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group content (C 3 -C 6) -carbonyl or C 3 -C 6 -alkoxyalkyl, (C 2 -C 6) alkylthioalkyl or C 2 -C 6 -alkyl or phenyl optionally substituted by 1 to 3 groups; (C 3 -C 8) alkylthioalkylsulfonyl or C 3 -C 8 cycloalkylsulfonyl; 7 carbon atoms, R is o a hydrogen atom or a cyano or C 1 -C 6 alkyl or C 3 -C 7 cycloalkyl or C 2 -C 6 acyl or alkoxycarbonyl group or a benzoyl group optionally substituted by 1 to 3 groups selected from R ?, R1 represents a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio-, haloalkylthio- or alkylsulphonyl group having 1 to 6 carbon atoms or a cycloalkyl, halo-cycloalkyl, alkenyloxy-, alkynyloxy-, alkenylthio- or alktnylthio- group containing 3-6 carbon atoms atom or nitro- or cyano- or amino group, optionally mono- or disubstituted (C 1 -C 6) alkyl or acyl, or (C 2 -C 6) alkoxycarbonyl, phenyl, phenoxy or pyridyloxy; be optionally substituted, or salts thereof, with the exception that when R and R ₂ simultaneously represent a phenyl group or simultaneously represent a methyl group, then B represents a CR 3 R 4 group, A represents a sulfur atom and W represents an oxygen atom or a sulfur atom, with the exception of the three compounds for which p wherein R @ 1 is hydrogen, n is 1, B is NR @ 1, R @ 2 and R _{@ 2} are methyl, AR @ 1 is SCH @ 1, W is oxygen and R @ ₂ is either hydrogen or methyl or is phenyl and R sloučeniny is phenyl, R ₂ , R ^ and R ^ are methyl, n is zero and A and W are both sulfur. Compounds according to claim 1 means a sulfur atom. Compounds according to claim 1 means an oxygen atom. of formula I wherein A is of formula I wherein W Compounds according to claim 2 of the general formula Ia (Ia) VII wherein W, n and R 6 to R 8 are as defined in claim 1. Compounds according to claim 2 of the general formula Ib in which W a to as defined in claim 1. Compounds according to claim 2 of the general formula Icr _{2 of} CH 1 N 4 (B) n R ₄ (Ic) wherein B, on R ₁ to R 6 have the meanings given in claim 1. Compounds according to claim 2 of the general formula Id Wherein B, n and R 1 are as defined in claim 1. Compounds according to claims 1 to 7, wherein R 1 represents a hydrogen atom. Compounds according to claim 5 of the general formula Ib, in which R represents a hydrogen atom (compound Ib). Compounds according to claims 1 to 9, in which R _{2 is} not a hydrogen atom. / Compounds according to claims 1 to 10, wherein R ₂ represents an alkyl group containing 1 to 3 carbon atoms. Compounds according to claims 1 to 11, wherein R 6 represents a phenyl group optionally substituted by R ₇ . Compounds according to claims 1 to 12, wherein R 1 represents an alkyl group containing 1 to 3 carbon atoms. - ^Ix 1 · 1. Compounds according to claims 1 to 13, in which R 6 represents a phenyl group optionally substituted by R 6 _? . Compounds according to claims 1 to 14, wherein R 1 represents a methyl group. Process (A) for the preparation of compounds of formula I according to claim 2, characterized in that alkylation of 2-thiohydantoins of formula R 1 X in the presence of a base is carried out by carrying out the compound II according to the equation CH) a base (ij solvent) wherein R, R ^, R ^, R ^, B and W are as defined in claim 1 and X represents a chlorine atom, a bromine atom or an iodine atom or a sulfate or alkylsulfonyloxy or arsulfonyloxy group. 17. A process for the preparation of 2-methylthio-2-imidazolin-5-one compounds of formula Ic (method B) according to claim 6, characterized in that the compound of formula V is cyclized by simply heating in the aromatic solvent to reflux temperature. flow according to the equation vz \ r ₂ ^R 1 ^Z N = C • SCH ₃ sch ₃ C-NH-CB) n R ₄ O (B) n-R ₄ sch ₃ wherein R 1, R ₂ , R, B and n are as defined in claim 1. A process for the preparation of compounds of formula V (method B) according to claim 17, characterized in that the iminodithiocarbonate of formula III is condensed with an amine or hydrazine of formula IV according to the equation sch ₃ 'SCHn. R ₄ - (B) n NH ₂ (TV) CO ₂ H (HD x = c ' ^SCH ' _{) 3} ^R 2x R _and C-NH (B) n R ₄ CO wherein R .j, R, R j _of Bam are as defined in claim 1, wherein it is essential that the acid III being activated for this condensation in the acid chloride form, in the dicyclohexylisourea form, using dicyclohexylcarbodiimide, or in the form of an imidazolide using carbonyldiimidazole. 19. A process for the preparation of compounds of the general formula Ib (process C1) XI - equation + R ₅ X Ib, characterized in that the compound of formula R 1 X is reacted in a solvent and in the presence of a base in reaction with a compound of formula Ib according to claim 5, wherein R 1 represents a hydrogen atom according to claim 9 (compound Ib), ₁ and Rf are as defined in claim 1 and in formula R is an alkyl group, an alkoxycarbonyl group, an acyl group, an aroyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group or a sulfamoyl group and X is a leaving group such as halogen , a sulphate group, an optionally substituted phenoxy group, an R 6 O group when R 6 represents an acyl group or an alkylsulfonyloxy group or an arylsulfonyloxy group or a non-leaving group such as an isocyanate group or an isothiocyanate group. 20. A process for the preparation of compounds of formula (Id) (process C2) according to the equation H. N <y SR ₃ R-N O + r ₂ x (B) n - R, Id XII, characterized in that the compound of formula Id according to claim 7, wherein R ₂ is a hydrogen atom (compound Id '), is reacted in a solvent and in the presence of a base at a temperature of -30 to 80 ° C with the compound of formula R Wherein X represents a chlorine atom, a bromine atom or an iodine atom and R 1 to R 3 and n are as defined in claim 1. 21. The method of claim 20, wherein the base is selected from the group consisting of an alkoxide, metal hydride, or amide, and the solvent is selected from ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, and aromatic solvents. A process for the preparation of compounds of formula I (method D) according to claim 1, wherein W is S = O, characterized in that S-oxidation of a compound of formula I in which W is a sulfur atom is carried out, The oxidation of 2-imidazoline-5-thiones is carried out with a stoichiometric amount of peroxides in the solvent at a temperature of -20 to 20 ° C. 23. The method of claim 22, wherein the peroxide is a peroxyacid and the solvent is selected from the group consisting of chloroform and methylene chloride. 24. Process for the preparation of dithiohydantoins of the general formula VI (method L) XIII in which R? ^and as defined in claim 1, characterized in that in the presence of a base, in a solvent and at a temperature of less than -60 ° C, two isothiocyanates of the formulas R ^R CHNR CHNCSCS and R ^NCS are reacted, wherein one of them is unable to form an anion. Method according to claim 24, characterized in that the base is selected from the group consisting of potassium tert-butoxide, sodium or lithium bis (trimethylsilyl) amide and / or alkali metal hydrides and the solvent is selected from ethers and cyclic ethers. A method according to claim 24 or 25, characterized in that R 1 and / or R 2 is an electron withdrawing group such as an aryl group, a substituted aryl group or an alkoxycarbonyl group. 27. The method of claims 24 to 26, wherein the isothiocyanate R &apos; NCS, which is incapable of forming an anion, is an aryl isothiocyanate. 28. A process for the preparation of 2-thiohydantoins of formula VII (Method F). XIV, characterized in that, prior to cyclisation, the reaction of a compound of formula IV with isothiocyanates derived from amino acids of formula VIII ^R 2 is carried out R _; -CN ₌ C = S CO ₂ R (VIII) wherein R 1, R ₂ , R 1, B and n are as defined in claim 1. 29. The method of claim 28, wherein the cyclization is performed by thermal heating of the mixture of reactants to a temperature between 110 and 180 [deg.] C. in an aromatic solvent such as toluene, xylene or chlorobenzenes. 30. The process of claim 28 wherein the cyclization is carried out using one equivalent of the base in a solvent at a temperature of -10 to 80 [deg.] C., whereupon the reaction mixture is subsequently neutralized at ambient temperature. 31. The process of claim 30 wherein the base is selected from the group consisting of an alkali metal alkoxide, an alkali metal hydroxide, and a tertiary amine, and the solvent is selected from ethers, cyclic ethers, alcohols, esters, dimethylformamide, and dimethylsulfoxide. 32nd Method (Method G) according to Claims 28 and 30, y. considerable ed t n characterized in that prior to the acquisition of 2-thiohydantoin derivatives by neutralization in an acid medium is used obec- alkyl halide of formula R 5 thereof, X, wherein X is Cl, Br ^J s F or I, or alkylsulphonyloxy or arylsulfonyl-N-oxy and R1 is as defined in claim 1 to form a compound of formula Id. : Compounds which are particularly useful as intermediates in the preparation of compounds according to claims 1 to 15 and have the general formulas II, III, IV, V, VI, VII and VIII (Π) · (ΣΠ) (3) n-NH, ( TV) R _; In 'SCH ₅ o ω H • (VI) H (VR) R, ^R, JCN ₌ C, _S, CO, R (VIII). 34. A fungicidal composition comprising, in combination with at least one agriculturally acceptable solid or liquid carrier and / or at least one agriculturally acceptable surfactant, at least one compound of formula I XVI ye. kWréw W represents a sulfur atom or an oxygen atom or an S-O group, Λ denotes an oxygen atom or a sulfur atom, n denotes 0 or 1, B represents a group NR 6 or an oxygen or sulfur atom or a group CR 1 R 8 or a group SO ₂ or a group C = O, R 2 and R ₂ , which are the same or different, represent a hydrogen atom, provided that one of the two groups is different from a hydrogen atom, or an alkyl or haloalkyl group containing 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or (C 2 -C 6) alkynyl or (C 3 -C 7) dialkylaminoalkyl or cycloalkyl or aryl comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinoline or methylenedioxyphenyl, each of which may be optionally substituted by 1 XVII to 3 groups selected from R ^ or arylalkyl, aryloxyalkyl, arylthio alkyl or arylsulfonylalkyl, in which the aryl and alkyl radicals are as defined above, or R 1 and R 2 together with the carbon atom to which they are attached may form a carbocyclic or heterocyclic group of 5 to 7 atoms, which groups may be condensed to a phenyl ring optionally substituted with 1 to 3 groups selected from R 6; . R @ 1 represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or 6-alkoxycarbonylalkyl or N N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an arylalkyl group in which the alkyl radical contains 1 to 6 carbon atoms and the aryl radical is a phenyl, naphthyl, thienyl, furyl or pyridyl group optionally substituted by 1 to 3 groups selected from meaning R ^, / R ^ represents a hydrogen atom when n is 1, or an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkoxycarbonylalkyl or N 3 to 6 carbon atoms; or XVIII N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, isoquinolyl or a methylenedioxyphenyl group, each of which may be optionally substituted with 1 to 3 groups selected from the group consisting of or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group in which the aryl and alkyl radicals are as defined above, or an amino group disubstituted by two or different groups selected from the group consisting of alkyl of 1 to 6 carbon atoms, alkoxyalkyl, alkenyl or alkynyl of 3 to 6 carbon atoms, cycloalkyl a group containing from 3 to 7 carbon atoms, an arylalkyl group as defined above, a phenyl group or a naphthyl group optionally substituted by 1 to 3 groups selected from R R, or a thienylmethyl or furfuryl group, a pyrrolidine, piperidine, morpholine or piperazine group optionally substituted alkyl having 1 to 3 carbon atoms, R _c stands for □ a hydrogen atom except when R R represents a hydrogen atom or an alkyl, haloalkyl, alkylsulphonyl or haloalkylsulphonyl group containing from 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulphonyl or 2-alkoxyalkylsulphonyl up to 6 carbon atoms; 5SBO '•' t.it'J. '.h't'-Jyú, ·· / .v'ľít'ó. :: νίΧ.ϊϊ *.> ·.'. - χιχ alkoxyalkoxykarbonylovou, alkylthioalkoxykarbonylovou or kyanoalkoxykarbonylovou radical containing 3 to 6 carbon atoms or a formyl radical or a cycloalkyl, alkyloxyacyl, alkylthioacyl, kyanoacylovou, alkenylcarbonyl or alkynylcarbonyl radical containing 3 to 6 carbon atoms or a cycloalkylcarbonyl group having from 4 to 8 Ublik _4-dumping atoms or phenyl. arylalkylcarbonyl, especially phenylacetyl and phenylpropionyl, arylcarbonyl, especially benzoyl optionally substituted with 1 to 3 groups selected from R _? , thienylcarbonyl, furylcarbonyl, pyridylcarbonyl, benzyloxycarbonyl, furfuryloxycarbonyl, tetrahydrofurfuryloxycarbonyl, thienylmethoxycarbonyl, pyridylmethoxycarbonyl, phenoxycarbonyl optionally substituted with (phenylthio) or (phenylthio) optionally substituted (phenylthio); , (alkylthio) carbonyl, (haloalkylthio) carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl, (furfurylthio) carbonyl, (tetrahydrofurfurylthio) carbonyl, (thienylmethylthio) carbonyl, (pyridylmethylthio) carbonyl or arylsulfonyl or carbamoyl, optionally mono- or disubstituted by a group selected from alkyl or haloalkyl of 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group of 2 to 6 carbon atoms or XX a phenyl group optionally substituted by 1 to 3 groups selected from sulfamoyl, a sulfamyl group optionally mono- or disubstituted by a group selected from alkyl or haloalkyl of 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group of 3 to 6 (C 2 -C 6) alkoxyalkyl, (C 2 -C 6) alkylthioalkyl or cyanoalkyl, optionally substituted by 1 to 3 R 3 groups; (C 3 -C 8) alkylthioalkylsulfonyl; or (C 3 -C 7) cycloalkylsulfonyl; R 1 is b a hydrogen atom or a C 1 -C 6 alkyl or C 3 -C 7 cycloalkyl or C 2 -C 6 acyl or alkoxycarbonyl group or a benzoyl group optionally substituted with 1 to 3 groups selected from R ^. R.? represents a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl group having 1 to 6 carbon atoms or a cycloalkyl, halo-cycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio group having 3 to 6 carbon atoms or a nitro or cyano group or an amino group of an optionally mono- or disubstituted C 1 -C 6 alkyl or acyl group or an C 2 -C 6 alkoxycarbonyl group, a phenyl, phenoxy or pyridyloxy group, which groups may be optionally substituted, and salts thereof. 35. A fungicidal composition according to claim 34 comprising 0.5 to 95% by weight of at least one compound according to any one of claims 1 to 15. 36. A method of treating crop plants infected with or threatened by fungal diseases, characterized in that an effective amount of a compound according to any one of claims 1 to 15 or a composition according to claim 34 or 35 is applied preventively or curatively. 37. A method according to claim 36, wherein the effective amount is 0.005 to 5 kg / ha. 38. The method of claim 37, wherein the effective amount is 0.01 to 1 kg / ha. /