FI119732B - Fungicidal 2-imidazolin-5-one and 2-imidazolin-5-thione derivatives and process for their preparation - Google Patents

Description

Fungicidal 2-imidazolin-5-one and 2-imidazolin-5-thione derivatives and process for their preparation

The present invention relates to novel imidazolinone or imidat-5-solininithione compounds which can be used for plant protection.

The invention also relates to processes for the preparation of these compounds as well as products which can be used as possible intermediates in these preparation processes. The invention further relates to the use of these compounds as fungicides (= antifungal agents), to the fungicidal compositions based on these compounds, and to methods for controlling plant fungal diseases using these compounds.

It is an object of the present invention to provide compounds having improved properties for the treatment of fungal diseases.

It is another object of the present invention to provide compounds having an improved spectrum of action against fungal diseases.

It has now been found that these objects can be achieved by the products of the invention which are 2-imidazolin-5-one and 2-imidazolin-5-thione derivatives of the general formula (I)! Λ 25 • ♦ · .Γ * Compounds comprising an imidazolinone or imidazoline ion group, • · · I. known for having the general formula (I) ♦ · · »» »» ». ^ »« · Α — R 3 φ 2 \ y ^ H <B> n — r4: ***: w (i) ··· '. Wherein: W is a sulfur or oxygen atom or a group S = O; A is O or S; n is 0 or 1; B is N (R5) or O or S or C (RS) (R6) or SO2 or C = 0; Rx and R2, which may be the same or different, represent: 2 - H, provided that either of these two groups is not H, or - an alkyl or haloalkyl radical of 1-6 carbon atoms, or 5 - 2- An alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical of 6 carbon atoms, or a dialkylaminoalkyl or cycloalkyl radical of 3-7 carbon atoms, including a phenyl, - ryl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl optionally substituted with 1-3 R 7 substituents, or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl, alkyl as defined above, or Rx and R2 may form the carbon atom to which they are attached t bonded to a ring, with a carbon ring of 5 to 7 atoms or a heterocycle which may be fused to a phenyl optionally substituted with 1 to 3 R 7 substituents; "· *. R 1 represents: a alkyl group of 1-6 carbon atoms, or alkoxyalkyl, alkylthioalkyl of 2-6 carbon atoms. 25, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl groups, or • · · · · · * - A dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group of 3-6 carbon atoms, or an N, N-dialkylcarbamoylalkyl group of 30 to 4-8 carbon atoms, or an arylalkyl group of 1 The radical having -6 carbon atoms and the aryl moiety is phenyl, naphthyl, thienyl, furyl or pyridyl optionally having from 1 to 3 substituents selected from R7; · 35 selected substituents; "* ·: R. means: 4 - a hydrogen atom when n is 1, or - an alkyl group of 1 to 6 carbon atoms, or 3 - Alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl, or alkynyl groups of 2-6 carbon atoms, or dialkylaminoalkyl of 3-6 carbon atoms, alkoxy-5-carbonylalkyl or 4-alkylalkyl, or -N-alkylalkyl; A Ν, am-dialkylcarbamoylalkyl group of -8 carbon atoms, or - an aryl radical including phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinoxyphenyl or isoquinolinyl, wherein Or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, the terms aryl and alkyl being as defined above, or - an amino group disubstituted with two identical or different substituents; - 1-6 carbon atoms incl Vän alkyl radical, - comprising 3-6 carbon atoms, alkoxyalkyl, alkenyl or 20 alkynyl, - a cycloalkyl radical comprising 3 to 7 carbon atoms, - the above definition arylalkyl • • · · according to the. , ·, A lir radical, a phenyl or a naphthyl radical optionally substituted with 1-3 R · 7 substituents. 25 tia, it • · · · ** | - a thienylmethyl or furfuryl radical, Tao R 4 represents a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted with 1 to 3 carbon atoms containing from 1 to 3 carbon atoms, : ***: R, stands for: · · · 3-H, except when R 4 is H, or • · - alkyl of 1-6 carbon atoms, of haloalkyl, of alkylsulfonyl- or a haloalkylsulfonyl radical, or alkoxyalkyl, alkylthioalkyl *: · *:, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, having from 35 to 2-6 carbon atoms, an alkoxyalkylsulfonyl or cyanoalkylsulfonyl radical, or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical having 4 to 3 carbon atoms, or a cycloalkyl containing 5 to 3 to 6 carbon atoms, alkoxyalkyl, a yl, cyanoacyl, alkenylcarbonyl or alkynyl lycarbonyl radical, or a cycloalkylcarbonyl radical of 4-8 carbon atoms or a 10-phenyl radical; arylalkylcarbonyl, especially phenylacetyl and phenylpropionyl; an aryl-carbonyl, especially benzoyl radical, optionally substituted with 1-3 R 1 substituents; tie-nyylikarbonyyli-; furyylikarbonyyli-; pyridyylikarbonyyli-; Benzyloxycarbonyl; furfuryylioksikarbonyyli-; tetrahydrofurfuryloxycarbonyl; tienyylimetoksikarbonyyli-; pyridyylimetoksikarbonyyli-; a phenoxycarbonyl or phenyl-thiocarbonyl radical, optionally substituted on the phenyl with 1-3 substituents selected from R 7; alkyl-20-thiolcarbonyl; halogeenialkyylitiolikarbonyyli-; alkoksial-kyylitiolikarbonyyli-; syanoalkyylitiolikarbonyyli-; benzyl · * · *; tiolikarbonyyli-; furfuryylitiolikarbonyyli-; tetrahydrofurfu- • ·. . ·. ryylitiolikarbonyyli-; thienylmethylthiolcarbonyl, pyridyl • · · ···; ·. a limethylthiolcarbonyl or arylsulfonyl radical, or • · · j. - a carbamoyl radical optionally substituted by a mono- or di-alkyl or halo alkyl group containing 1-6 carbon atoms, or - 3; Cycloalkyl, alkenyl, or alkynyl groups containing -6 carbon atoms, or alkoxyalkyl, alkylthioalkyl or cyanoalkyl groups containing 2-6 carbon atoms, or • ♦. - phenyl, which may have from 1 to 3 Rj in the intermediate. or 35 R5 represents * "*: - a sulfamoyl group optionally mono- or disubstituted with an alkyl or haloalkyl group of 5 to 1-6 carbon atoms, or a cycloalkyl, alkenyl or 3-6 carbon atom; an alkynyl group, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group of 5 to 2 to 6 carbon atoms, or a phenyl optionally substituted with 1 to 3 R 7, or R 5 represents an alkylthioalkylsulfonyl of 10 to 3 to 8 carbon atoms; A cycloalkylsulfonyl group containing from 7 carbon atoms; R6 represents: a hydrogen atom or a cyano group or an alkyl group having from 15 to 1 to 6 carbon atoms or a cycloalkyl group having from 3 to 7 carbon atoms, or an acyl or alkoxycarbonyl group having 2-6 carbon atoms; optionally having from 1 to 3 substituents selected from R3; R7 represents: · * · ': - hydrogen - alkyl radicals of 1-6 carbon atoms, alkyl, haloalkyl, alkyl, coke, haloalkoxy, alkylthio, haloalkylthio, or • · ·: * 1 * I - A cycloalkyl, halo-cycloalkyl, halo-cycloalkyl, alkenyloxy, alkynyloxy, alkenylthio, or alkynylthio radical containing from 3 to 6 carbon atoms, or a nitro or cyano group, or • · * * *: 30 - an amino radical optionally mono- or disubstituted with an alkyl or acyl radical of 1-6 carbon atoms or an alkoxycarbonyl radical of 2-6 carbon atoms, or ·. - a phenyl, phenoxy or pyridyloxy radical optionally substituted with 35; ***** and salts thereof, except for compounds wherein B is C (R 5) (R 6), A is sulfur and W is O or S when R 3 and R 2 are simultaneously phenyl or simultaneously methyl; with the exception of three compounds wherein R 3 is hydrogen, n is 1, B 5 is NR 4 when R 5 and R 4 are methyl, AR 3 is SCH 3, W is 0 and R 2 is either hydrogen, methyl or phenyl; except for the compound wherein R 3 is phenyl, R 2, R 3 and R 1 are methyl, n is 0 and A and W are both sulfur atoms; with the exception of compounds of formula (I) wherein: 10 to n = 0; and - R 1 and R 3 are simultaneously methyl; and - A is a sulfur atom; and - R4 is phenyl substituted by two groups, one of which is selected from the group consisting of a cyano group, a nitro group or a ha-15 logene atom; the other is selected from trifluoromethyl or halogen; likewise, with the exception of the following compounds: - 3 - [(4-chlorophenyl) sulfonyl] -3,5-dihydro-2-methoxy-5-20 methyl-5- (1-methylethyl) -4H-imidazol-4-one; - 2- (ethoxycarbonylmethylthio) -3-acetyl-5,5-diphenyl-3,5-dihydro-4H-imidazol-4-one; . - 2-butoxy-5-ethyl-3,5-dihydro-3-methyl-5-phenyl-4H- · · ··· imidazol-4-one; • · · '. 25-2-methoxy-5-methyl-3,5-dihydro-3- (1-phenylethyl) -4H-2 · 2 · 2-imidazol-4-one; • 2- (methylthio) -5,5-dimethyl-3,5-dihydro-3-phenyl-4H-4H-imidazol-4-one; - 2- (methylthio) -3,5,5-triphenyl-3,5-dihydro-4H-imidazol-4-30 one; - 3-methyl-2- (methylthio) -1,3-diazaspiro [4,5] dec-1-en-4-one; - 3-methyl-2- (methylthio) -1,3-diazaspiro [4,5] dec-1-ene-4-thione.

• ·. and salts of these compounds.

Certain specific compounds of formula I, i.e., compounds of formula Ia are known.

• · 7 R2V SR3 H (C) n-R4

w I

Re (1a) wherein W, n, R 1, R 4 are as defined above in connection with Formula I.

The essential features of the invention are set forth in the appended claims.

In particular, the following discloses the pharmacological properties of S-alkyl derivatives of 5,5-diphenyl-2-thiohydantoin and S-alkyl derivatives of 5,5-diphenyldi-10-thiohydantoin: a) Zejc, A., Dissertationes Pharmaceuticae et pharmacoloqiae.

Warsaw, 20 (5), 507-524 and 525-537 (1968) b) Luca-Sobstel, B. (Zejc, A.Dissertationes Pharmaceuticae et 15 Pharmacolocriae, Warsaw, 22 (1), 13-19 (1970). c) Fetter, J., Harsanyi, K., Nitrai, J., Lempert, K., Acta Chemica (Budapest), 78 (3), 325-333 (1973).

No fungicidal activity has been described for these compounds.

Other specific compounds of formula I have been described in Böhme, Martin and Strahl, Archiv der Pharmazie, 313, 10-15. (1980) (Ref. D). These are 3 of the following compounds: 25-CH3-CH2 = H, CH1-phenyl

• \ I

f T

::: ch, ··· Φ 3 • · · * ... · 30 These compounds are included in the compounds of formula Ib which are part of the present invention: • ♦ iVi I (Ib) • * 35 ^^ n-r4 wj R5 Wherein W and R1-R5 are as defined in formula I.

Compounds of Formula Ia may be prepared by methods known per se, as described in the above references and in the following references: e) Biltz, H., Chemische Berichte, 42, 1792-1801 (1909), f) Chattelain, M. and Cabrier, P. ., Bulletin de la Societe Chimicrue de France. 14 (1947), 369-642, 10g) Carrington, C.H., Warring, W.S., Journal of the Chemical Society. (1950) 354-365, h) Lampert, K., Breuer, J., Lemper-Streter, M., Chemische Be richte. 92, 235-239 (1959), i) Shalaby, A., Daboun, H.A., Journal fur Praktische Chemie. 313 15 (6), 1031-1038 (1971), j) Simig, G., Lemper, K., Tamas, J., Tetrahedron, 29 (22), 3571-3578 (1973), k) Schmidt, U. , Heimgartner, H., Schmidt, H., Helvetica Chemica

Acta. 62 (1979), 160-170, 20 1) Muraoka, M., Journal of 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 prepared by the method described by Böhme, Martin and Strahl, Archiv der Pharmazie. 313, 10-15 (1980) (ref. D), or by one of the methods described below: • ♦

Method As A process for preparing compounds of formula (I).

Preparation of Compounds of Formula (I) by S-Alkylation with 2-Thio-. the hydanthines (II) proceed according to the following reaction equation:

B

• · R2 \::: 2 \ / ^ · ♦ · · base 'Τ' + RaX solvent * "(I) *: * ·: ff JB) n-R4 w. ·. 35 (II) • · · * · * ·] Where X represents a chlorine, bromine or iodine atom or a sulfate ♦ · · · · group or an alkylsulfonyloxy or arylsulfonyloxy group, the alkyl and aryl being as defined above for R 1 and R 2 The base may be an alcoholate, for example potassium tert-butylate, an alkali or alkaline earth hydroxide, an alkali carbonate or a tertiary amine. The solvent may be ethers, cyclic ethers, alkyl ethers, acetonitriles, 1-3 carbon atoms, , for example tetrahydrofuran, at a temperature of -5 to +80 ° C.

This method can be used for compounds wherein W represents a sulfur or oxygen atom.

The 2-thiohydantoin of formula (II) can 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) 681-20686, g) Carrington, C.H., Warring, W.S., Journal of Chemical Soc. (1950) 354-365, • · «• V h) Lampert, K., Breuer, J., Lemper-Streter, M., Chemische Be-

Ijfi richte, 92, 235-239 (1959), 25 i) Koltai, E., Nitrai, J., Lempert, K., Buries, L., Chemische •; Berichte. 104, 290-300 (1971), ··· ·

: or one of the two methods described below

Or F, which are part of the present invention.

• · · * ... Method B: Preparation of Ie.

Preparation of 2-Methylthio-2-imidazolin-5-ones of Formula (Ie) by Cyclisation of Iminodithiocarbonate of Formula (V) - - - - - - - - - - - - - - - - - - - - - · .1 ··. tions proceed according to the following general scheme: · a ♦ R2 NH2 base + cs2 + 2ch3i ------->

Ry X CO 2 H 5 b) / SCH, R, - (B) n -NHp .SCH,% N = <3 '(IV) 2 R, N = <io V / \ sch5 ----------. -> W sch3

Ry C02H / \

Ry X> NH- (B) n -R 4

(III) O

(V) 15 c) / SCH3 R2 N = C δ R2 20 V / SCH, ------> \ y \ / \ / N.

Ry-c-NH- (B) n -R 4 - (B) n -R 4 O (V) 25 (Ic) a) Iminodithiocarbonates (III) can be prepared by operating under the conditions described in the literature for analogous compounds: ... -C. Alvarez Ibarra et al., Tetrahedron Letters. 26 (2), 243- «· *; * 246 (1985), '« · * -E. Melendet et al., Synthesis. 1981, 961, m 9: '· According to the following reaction equation: | i': 35 R 2 NH 2 base ·: X + cs 2 + 2ch, i ---------> (in)

** R, COpH

(B) Compounds of formula (V) are obtained by condensation of compounds of formula (III) with amines or hydrazines of formula (IV). To enhance the condensation, the acid (III) must be activated to the dicyclohexylisourea acid chloride · · · · dicyclohexylcarbodiimide or% imidazolidic acid: * 45% carbonyldiimidazole. Condensation is carried out on these types of compounds under normal conditions.

C) The cyclization of the compounds of formula (V) is effected simply by heating in an aromatic solvent while refluxing. In particular, xylene, chlorobenzene or dichlorobenzene can be used as the solvent.

5

Methods C: Formation of derivatives Ib ') and (Id ·) ·

Method Cl: Preparation of Ib by Compound Ib 'N-Derivative.

Compounds of formula (Ib ') [compounds (Ib) wherein R 5 represents a hydrogen atom] may be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulfamoylated according to the following general reaction equation: R 2 -SR, base R 2 -SR, \ / η solvent V /

Λ + r5x ---------> I

20 R (\ ___R.

r ^ n-r4 f \ N-r4 w I w | H R g 25 Ib 'Ib ??????????? R 5 ??????????? R 5 ????????? ?????????? ?????????? ???????????? ?????????????? ?????????? ?????????? ?????????? ???????? ??? arylsulfonyl, carbamoyl or sulfamoyl.

X represents a halogen, optionally substituted sulfate or phenoxy group, or an alkylsulfonyloxy or arylsulfonyloxy group, or R 50 when R 5 is acyl.

• · * · * 35 I · *

Alkali hydrides, alcoholates or ··· tertiary amines may be used as the base. The reaction may be carried out at a temperature in the range of -30 ° C to 50 ° C. As the solvent, for example, ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents may be used.

• «12

The carbamoylation of the compounds (Ib ') may be accomplished by reaction with isocyanates or isothiocyanates according to the following reaction equation: 5 R-. SR ·, R? . ^ SR,

V V

/ \ I + r5-n = c = y ----> A, I

R! Rf \ ___- N \ S n-r4 Γ ^ n-R4 10 w w

B

Y nhr5

Ib 'Ib 15

However, the reaction is carried out under the conditions described above so that the base can be used in a catalytic amount.

Method C2: Preparation of Compounds Id

Compounds Id '(compounds Id where R2 is a hydrogen atom) can be alkylated at position 4 according to the following reaction equation: 25 Hv ^ -SR3 base R2 ^ SR3 \ / ^ 11 solvent \ y

A + r2x ------> A I

R1 R1 \: VA (B) n "R4 A ^ - (B) n-R4.. · Β0 oo '• · · • · Φ: Id' Id • · · • · · tt ·. ·. 25 • X represents a chlorine, bromine or iodine atom The base may be an alcoholate, a metal hydride or an amide The reaction may be carried out at a temperature of -30 to +80 ° C.

Ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents may be used as the solvent.

· · 13 13 13 13 13 13 13 13 13 13 13

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

Compounds of formula (I) wherein W represents S = 0, 5 are obtained by oxidation of 2-imidazoline-5-thions according to the following reaction equation: R2i / N ^^ AR3 R2 / N ^ / AR3 \ / oxidant \ /

io ---------> Λ I

Ri Ri # ^ (B) n -R 4 ^ (B) n -R 4 s s, 15

Peroxides, in particular peracids, may be used as the oxidizing agent. The oxidant can be used in a stoichiometric amount. The oxidation is carried out in chloroform or methylene chloride at a temperature in the range of from 20 to 20 ° C.

Method E: Preparation of dithiohydantoin of formula (VI)

The dithiohydantoin of Formula (VI) may be obtained by administering alpha anions of isothiocyanates, which do not form anions, according to the following reaction equation: • · ·

• · · TT

··· H

• * · * R2 R2 / N v / S

: .30 | base \ /

: .j: R1-CH-N = c = s + R4-N = C = S -------------> I

. *. : solvent R

*: ./ K r4 • · · c • · · '35 (VI) • · · · ·'} At least R1 or R2 must be an electron withdrawing group (such as aryl, substituted aryl, alkoxycarb [ · "Banyl, etc.). The isothiocyanate R4-NCS must not form anions -" "and; aryl isothiocyanates are particularly well suited for this reaction.

• «· • · · • • • • • 14

As the base, potassium tert-butylate, lithium bis- (trimethylsilyl) amide, alkali hydrides may be used. As the solvent, ethers, cyclic ethers, may be used. The reaction is carried out at a temperature below -60 ° C. The anion can be captured 5 as it is formed. For this purpose, the mixture of the two isothiocyanates is poured into a basic solution at a temperature below -60 ° C.

Method F: Preparation of 2-thiohydantoin of formula VII) Preparation of 2-thiohydantoin (VII) starting from the isothiocyanate obtained from amino acids (VIII) is carried out according to the following reaction equation:

B

15 R, R, / Nv. yS

i \ / R 1 -C-N = C = S + R, - (B) n -NH 2 -------> \ I R 1 CO 2 R Λ (B) n -R 4

20 O

(VI)

The cyclization can be carried out in two ways: thermally, whereby the reactant mixture is heated to a temperature in the range of 110-180 ° C in an aromatic solvent, such as toluene, xylene, chlorobenzene; J.j.J., in a basic environment in which one equivalent of a base such as an alkali alcohol, an alkali hydroxide or a tertiary amine is present. Under these conditions, the cyclization is performed at a temperature in the range -10 ° C to +80 ° C.

• ·

As the solvent, ethers, cyclic ethers, alcohols, esters, DMF, DMSO and the like can be used. via.

[* 35] Isothiocyanates may be prepared by any of the methods described *: * in Sulfur Reports, Vol. 8 (5), pages 327- · · ·: ***: 375 (1989).

• · ♦ ·· ♦ • · · • ♦ «· ♦ · 15

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

When the cyclization of the 2-thiohydantoin is carried out according to Method F5 under basic conditions, after completion of the reaction, the thiohydantoin is in the form of a thiolate which can be reacted directly with an alkyl halide or sulfate R3X or with R3X where X is alkylsulfonyloxy or arylsulfonyloxy . Thus, Methods A and F can be combined according to the following reaction equation:

Rp R? / N ^ S "M + I 5" M + \ / 15 R1-C-N = C = S + R4- (B) n-NH2 -------> / \ | I Rl Y ^ N \ C02R Jr ^ (B) n-R4 0 20 r2 / n ^ s-r3 _____> X 1 25 ^ ^ (B) n-R4 0 (I) »· · • · • * Method Q: Preparation of Compounds of Formula Ie, wherein (B) n is a sulfur atom. * 30 * These compounds can be obtained by reacting sulfuryl chloride R4SC1 with an imidazolinone of formula IX. according to the following reaction equation: I '··· 5 VNXS "base VV"'

... X \ I + r4sci --------> χ \ I

; r (\ ^^ NH solvent \ ___— N'v.

f // s \ o o ^ r4 ··· Y (IX) (le) »« · • · · *. 45 • · 16

The reaction is carried out at a temperature in the range of -20 to +30 ° C in the presence of one molar equivalent of base. As the base, alkali hydrides, alkali alcoholates or tertiary amines may be used. Polar 5 solvents such as ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide or aromatic solvents may be used as the solvent. The imidazolinones (IX) can be prepared analogously as described in Method A.

Preferred compounds for improved fungicidal activity and / or ease of synthesis are: 1) compounds of formula Ib, 2) compounds of formula I, especially Ib, wherein R 5 is a hydrogen atom, 3) compounds of formula R 1 and R 2 other than H , 4) compounds of the formula wherein R 2 is an alkyl group of 1 to 3 carbon atoms, 5) compounds of the formula R 1 represents a phenyl ring optionally substituted with R 7, 6) compounds of the formula R 3 represents an alkyl group of 1 to 3 carbon atoms, 7) compounds of the formula wherein R4 represents a phenyl core optionally substituted with R7. 8) compounds of the formula wherein R 3 represents a methyl group.

• · ·: ·. The following examples are intended to illustrate the invention. , their methods of preparation and their fungicidal properties.

• · · · · · 30 The structure of each product is confirmed by one or more of the following spectrometric techniques: 1 H-NMR Spectrometry: H-NMR, C-NMR Spectrometry, Infrared Spectrometry or Mass Spectrometry.

············································································································································· 35! .) or fold multiplier (dD20).

Example 1 Preparation of Compound 34 According to Method A 0.9 g (3 mmol) of 3-benzyl-5-methyl-5-phenyl-2-thiohydantoin is dissolved in 30 ml of anhydrous tetrahydrofuran. The reaction mixture is cooled to 0 ° C and then 0.34 g (3 mmol) of potassium tert-butylate is added. The reaction mixture is allowed to react for 10 minutes at 0 ° C, after which 0.46 g (3.3 mmol) of methylene iodide is added dropwise at this temperature; potassium iodide is precipitated. The reaction mixture is allowed to warm to room temperature. The mixture is diluted with 100 ml of 15 ml of ethyl acetate. Wash the solution twice with 100 ml water each time. The solution is dried over sodium sulfate and then treated with activated carbon. The solution is concentrated under reduced pressure; 0.6 g of 1-benzyl-4-methyl-2-methyl-lithio-4-phenyl-2-imidazolin-5-one (Compound 34) is obtained in the form of a pale yellow solid, m.p. 68 ° C. C.

In the same manner, the following compounds ** · 1 have been prepared: 25 R, .SR,

Li / Xl,: ··! (O) W1

.1; 1.30 w I

• · · 1 R5 • · • • t · • • • • • • • • • • • • • • • • • • • • • • • • • • • • •• 35 · • υ υ υ υ υ υ

r- o m ^ oco ^ NNOLnmn ^ m ^ Mcoooinci ^ r'OwwoNVJO

n n • «ίοοιΟιΗ ^ ιτισιίΝσί '^ Γ'Μ' MnnffiHinnH'i'fhHcomon

rH rH iHrHrHrHiH H rH H ^ H H rl rH rHrHrHiHrHrH H H

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

».............. S .................

P aa aCUCUCUaQtCUCUCUCUaaQ afUCUaaCUftaCUaCUCUCUaaa u ιηω o303ö3a) ojo3 03 0) ö3 03 0) 03 G03030) 03030303030J03030) 0303ö303

£ en en OOOOOOOOOOOOOOOOOOOOenOOenOOOOO

•B

rH

> 1> 1

I-P

in <u "m.". <u tn <u

H K

o

• H - Il H

rH | · Η JXj fi

• H * H Ή J> i ^ ^ ^ · Η · Η -rH -H rH O O

H H 43 H 43 4 * t> 1 CU Λ CU H rl rl H I I 3

> 1> i CU ΪΡ CU CU -P I -H -H> 1> 1> i> i> i · Η -H CU

> 1> 1 -H> i-rl -H G-h 03 03 · Η43> ι> ι> ι> ιΉ rH Η I

H H p H U P £ P X 4ί H P, fl Ό Ό fl O> t> 1 <N

OO O OO OO O O> ι I -H -rl -H -H 03> i> iO

-P-P 3 -PO 0 · 0 -P 43 Nn U U U U-P Ό TS en

* · *. (ö (0 rH O H rl 4-J I-I Q) <0-P0> (i> 1> 1> l0 -H -H

• · -ppu-i-p ^^ p * g g as s a a a a-π p p

• * * · 43 43 X! <D (0X! IX! PIX3IQ) I 43 43 l43IO) llll | .p43> i> i <D

. Pi CU CU CU g CUCU -sfCU O n CU # -P N CUCU ^ CUnjfö ^ njnjnn I CUCU ag

m III

.. n {m h · • · * * «

«· -H

:::> h -h

»·» ·> 1 rH

. ·. : -h> i> 1: i h -h a> i * · O> 1 rH o a os> i> i p o en • · · m a s, a p m * oo .no a en ip en en en

n 0) 1 PQ) Q3 (D-Pa) rH (l) (l) 03Q3 (DQ) (U (D (D (DI Q) Q) Q) (UQ3 (DQ3C1) W <1) (1) QJ

ps gnj aggsws <sg-Hsssgggscssgsgggsejsgg * · · • · · · · MQ) (D a) Q) Q) (DQ) (l) (DQ) Q) <Da) (D (UQ) Q) a) Q) (l) (l) a) (D (l) <UQ) <l) (U <l) Cl) (l) ... «gg ggggggggggggggggggggggggggggg • · • • • • • • • •. ·

·; ·; O HcM dOHNn ^ iniOhcomOripm ^ inoHn ^ iniOMoinoHN

5 HHrlrlrlrlrlrHHrlOlfHOKMMNH'H'H '^' i ^^ r'hOOlOa) in o in o in o

rH rH (M f \) CO

(O {O {O {O (O

P P P P

n tn wwm UUUUUUUUUU ^ -H-HU-HH oooooooooolOfljnjo {0 (0> gggg about ^ otoootowH (0 (0 ^ <o (0 <Ν (Να3 ·> 3 ·> ΐΓ) Γ ^ ΐΓ)) νο> · η · η ^ · η · π HH HH {N II {0 {0 H {0 {0

Il II II II II II II II II II 'CC II cc ai .......... 8 p 3 · 3 3 P ΟηΟηΟη £ ΙηΡΙηΟηΟη £ Ιη & η £ ΙηΩ.ϊϊ> Ρ ftil i3 a ininininininininin = ra: :

is «BMMOOOOOOOOOMOO

m ai ei iiiiiiiiEEgmiEn.i σ> ω h ^ ffi

U

C OOOOOOOOHHHHOOHO

•B

'H rH

·· ·. Ή · Η> i. :> 1 rH>,

• *> 1> lO

. G> 1 · Η Λ ai p p {¾

.. -H 3> i O

• * P <W Oh g: * · ^^ xipaiaipaiaipxiiQiiiaixji

. . Pi ei Ph Ph g g Λ g g Ph CU CM g {M CO g Oh {N

• · · L

** ♦ · G

• · ^ • ·· Ph m * U —Pi ·> · ro ”* ° \ / co w en N, -ä ro {υαιφαίφφαιοιφφαίφφφφφ n \ ei gggggggggggggggg: * · *: / \ χ Ä • * * X / ' l> • χ ^ /

• X

• / \ «·· / x ...: cm> ---- s. oj ai p ai p ai ρ αιαιαιαίφραια) ... Pi / / ^ s \ Ρί gpHgPcggpHggggggpHgg (O /

• \ J

• · · • · * • · • · • · · · ·; O wr'COOioHNdcfin «)> {oo {Mh g {NKMrjoinnnnnnnnnimnin tn o in o io o h h cn nj n 20

Similarly prepared: 4- (3-pyridyl) -4-methyl-1- (N-phenylamino) -2-methylthio-2-imidazolin-5-one (Compound 51; m.p. = 156 ° C); 4-Phenyl-4-methyl-1- (benzyloxy) -2-methylthio-2-5 imidazolinone (Compound 56; from honey).

Example 2

Preparation of Compound 7 according to Method B 10 a) N- [Bis (methylthio) methylene] -2-phenylglycine [Compound (III) wherein R 1 = phenyl and R 2 = H] 100 g (0.66 mol) of phenylglycine are dissolved in + 5 ° C. At 33 ° C, 335 g (1.3 mol) of a 22% aqueous solution of potassium carbonate. 55.3 g of sulfur carbon are added to the mixture with vigorous stirring. A precipitate appears in the reaction mixture and turns orange in color. The reaction mixture is allowed to react for 3 hours at room temperature, after which 103 g (0.73 mol) of methyl iodide are added while maintaining the reaction temperature below 30 ° C. The mixture is allowed to react for 0.5 hour, then 74 g (0.66 mol) of a 50% solution of potassium carbonate are added. The reaction mixture is allowed to react for 0.5 hours, after which 103 g of methyl iodide is added again and the reaction mixture is given an ** - *; react for 1 hour. Dilute reaction mixture to 300 · ·

. ml of water. The reaction mixture is acidified to pH 4 IN

j *. 25 with hydrochloric acid. The product is extracted with 500 ml of ethyl acetate.

The solution is dried over magnesium sulfate and then concentrated • · ♦ [Γ | under reduced pressure. 49.5 g of N- [bis · ·· * .. * (methylthio) methylene] -2-phenylglycine (31% yield) are thus obtained in the form of a yellow solid with a melting point of 112 °. C.

30 ··· ί V b) [N- [Bis (methylthio) methylene] -2-phenylglycyl] -meta-chloro-η * V: Riphenylhydrazide (Compound V where R 1 = phenyl, R 2 = H, R 4 = metachlorophenyl, n = 1, B = NH) [···. To a solution of 2.95 g (16.4 mmol) of N- [bis (methylthio) -4,5 * methylene] -2-phenylglycine in 40 ml of methylene chloride is added. 3.38 g (16.4 mmol) of dicyclohexylcarbodiimide, after which the reaction mixture is allowed to react for 0.5 hours at room temperature. To this is added 2.34 g (16.4 mmol) of methachlorophenylhydrazine. The reaction mixture is heated to 0, 5 hours at 30 [deg.] C. The insoluble material is removed by filtration.

21

Wash the filtrate twice with 30 ml water each time. Concentrate solution 5 is obtained to give a honey-like substance which is purified by chromatography on silica gel. After purification, 2.5 g of [N- [bis (methylthio) methylene] -2-phenylglycyl] -methachlorophenyl hydrazide are obtained as a pink powder, m.p. 146 ° C.

C) 1-Methachlorophenyl-2-methylthio-4-phenyl-2-imidazolin-5-one (Compound 7) 1.92 g (5 mmol) [N- [bis (methylthio) methylene] -2 -phenylglycyl] -meta-chlorophenyl hydrazide is dissolved in 30 ml of xylene-15. The reaction mixture is heated under reflux for 4 hours. The reaction mixture is concentrated under reduced pressure. The resulting honey-like substance is rubbed in 10 ml of ether to crystallize the product. The precipitate is filtered off and the product is dried in a vacuum desiccator. In this way, Compound 7 is obtained in 56% yield as a yellow powder with a melting point of 196 ° C.

! 1 · 1 ♦ In the same manner, the following compounds were prepared: · · • i ··: ·. 25: R2 • · · \ / · «· ♦ \ s1 ·.: VJ30 (O) 1! wi R5 ·· «• ♦ ·« »• · ··« • · r— ·. · 13 5 »I · ···« «·· • · • · · · ..1.40 • · · # ·• «1 · 22 NO. R2 R3 R4 R5 W Cte

4 H Me 2-ChloroPh H 0 mp = 130 ° C

5 H Me Ph HO mp = 190 ° C

5 6 H Me 4-chloroPh H O mp = 162 ° C

7 H Me 3-chloroPh H O mp = 196 ° C

8 H Me methatolyl H 0 mp = 182 ° C

59 H MeS 2,4- (CH 3) 2 Ph H 0 Mp = 64 ° C

61 H MeS 2.5- (CH 3) 2 Ph H 0 Mp = 162 ° C

10 63 H MeS 2-EtPh H O mp = 126 ° C

69 H MeS 2.5- (01) 2 Ph H O mp = 144 ° C

71 H MeS 3,5- (01) 2 Ph H O mp = 146 ° C

In a similar manner, 4-phenyl-1- (N-phenylamino) -2-methylthio-2-imidazolin-5-one (Compound 120) was prepared.

Example 3 Preparation of 4-methyl-1- (N-methyl-N-phenylamino) -2-methylthio-4-phenyl-2-imidazolin-5-one (Compound 22) by alkylation (methylation) according to Method Cl.

A solution of 1 g (3.2 mmol) of 4-methyl-1-phenylamino-2-methylthio-4-phenyl-2-imidazolin-5-one in 30 ml of anhydrous tetrahydrofuran is cooled to 0 ° C, add 0.4 g (3.5 mmol) of potassium tert-butyl · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · sheet. The reaction mixture is allowed to react for 0.5 hours at 0 ° C. 0.5 g (3.5 mmol) of methylene iodide are then added thereto, after which the reaction mixture is allowed to react for 0.5 hours at room temperature. The reaction mixture is poured into 100 ml of water and the product is extracted with 100 ml of diethyl ether. The ether solution is dried over magnesium sulfate and concentrated. The product crystallizes when rubbed with 10 ml of diisopropyl ether. It is filtered and ... dried in vacuo. In this way, 0.73 g (70% yield) of · · · * .. * 35 are obtained as a pale yellow powder with a melting point of · · · 124 ° C.

• · ♦ ···· · ♦ · • • • • · · M · • · ·: * 40 ♦ • · 23

Example 4 Preparation of 4-methyl-1- (N-acetyl-N-phenylamino) -2-methylthio-4-phenyl-2-imidazolin-5-one (compound 23) by acylation (acetylation) according to Method Cl.

A solution of 1 g (3.2 mmol) of 4-methyl-1-phenylamino-2-methylthio-4-phenyl-2-imidazolin-5-one in 30 ml of anhydrous tetrahydrofuran was cooled to 0 ° C. To 0.4 g (3.5 mmol) of potassium tert-butyl 10 -ateate. The reaction mixture is allowed to react for 0.5 hours at 0 ° C. 0.25 g (3.5 mmol) of acetyl chloride is then added thereto, after which the reaction mixture is allowed to react for 0.5 hours at room temperature. The reaction mixture is poured into 100 ml of water and the product is extracted with 100 ml of diethyl ether. The ethereal solution is washed to neutral with water. It is dried over magnesium sulphate and then concentrated. This gives a honey-like substance which is purified by chromatography on a silica gel column. The purified product is crystallized from diisopropyl ether. 0.25 g of compound 23 are thus obtained in the form of a white powder having a melting point of 132 ° C.

In a similar manner, compounds 39 and *: 42 were prepared.

R / SR3 r? 5 \ / ^ r

(O) w-I

WELL. R2 R3 RS «cte • ·

: ':' Δ5 23 Me Me P * 1 methyl O m.p. = 132 ° C

*. 39 Me Me ph formyl O "honey jamaine".:. 42 Me Me ph tBuOCO O "honey jamaic" ···· «·« • * • · • · ·: -.- 40 • · * • · 24

Example 5 Preparation of 4-Ethyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (Compound 48) according to Method C2 5 To a solution of 1.5 g (5.50 mmol) of 2- methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound 5) in 50 ml of anhydrous tetrahydrofuran, 0.55 g of potassium tert-butylate is added. The reaction mixture is allowed to react for 30 minutes at room temperature, after which 0.8 g of 10 (5.05 mmol) ethyl iodide is added. The reaction mixture is allowed to react for 1 hour at ambient temperature. The reaction mixture is diluted with 150 mL of ethyl acetate. The solution is washed with water and then concentrated under reduced pressure. The product is purified by column chromatography over silica gel (silica gel: Merck 60H; eluent: ethyl acetate 25% / heptane 75%). 0.65 g of compound 48 is thus obtained in the form of a light brown powder having a melting point of 147 ° C.

By the same procedure, compound 49 is obtained.

20 ν-'γ "· lii» CA-V "

·. w I

I; ^ • · · • · · · · · · · -i30 • · · '· *: No. R2 R3 R4 R5 W Cte

... 48 Et Me Ph HO mp = 147 ° C

• * .S5 49 isoPr Me Ph H 0 mp = 135 ° C

... «O Me MeS 2,4- (Me) 2Ph H O" honey jamaine "

62 Me MeS 2; 5- (Me) 2 Ph H O m.p. = 160 * C

*. 64 Me MeS 2-Et Ph H O "egg jamaine"

65 Me MeS 2,4- (Cl) 2Ph H O

: '** 40 66 MeS 1-naphthyl H 0 mp = 174 ° C

70 Me MeS 2.5- (Cl) 2 Ph H O m.p. = 180 ° C

:. · ·. 72 Me MeS 3,5- (Cl) 2 Ph H O m.p. = 200 ° C

M.p. = 124 ° C

·: ··: 79 Me MeS 2-CF 3 -PH H O m.p. = 91 ° C

45 25

4-Methyl-2-methylthio-4- (4-fluorophenyl) -1-phenylamino-2-imidazolin-5-one (Compound 68) was prepared in a similar manner.

Example 6

Preparation of Compound 2 according to Method D 1 to 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: chloroform. After cooling to -10 ° C, a solution of 1.35 g (5.5 mmol) of meta-chloroperbenzoic acid in 30 ml of chloroform is added over 10 minutes. After this addition is complete, the reaction mixture is allowed to warm to room temperature.

The reaction mixture is washed with a saturated aqueous sodium bicarbonate solution and then with distilled water. The organic phase is treated with activated carbon and concentrated. The resulting honey-like substance is mixed with 20 ml of ether to dissolve the honey-like substance first, followed by precipitation of a light-brown solid. The precipitate is filtered. The product is dried under reduced pressure. This gives 0.4 g (25% yield) of ··, ·, 2 as a light brown powder with a melting point of 150 ° C.

• · • · • · · NO. R2 R3 R4 R5 W Cte • ·

; 1 * 25 2 Me Me Ph H S = 0 mp = 150 ° C

EXAMPLE 7 Preparation of 3,5-Diphenyl-5-methyl-dithiohydantoin according to Method E:?. 15.1 g · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · (122 mmol) of potassium tert-butylate is dissolved in 200 ml of tetrahydrofuran. This solution is cooled to -70 ° C.

• ·

A solution of 20 g (122 mmol) of alphamethylbenzyl • isyl thiocyanate, 16.55 g (122 mmol) of phenyl isothiocyanate is added dropwise, maintaining the temperature below 35 ° -60 ° C. and 50 ml tetrahydrofuran. After the addition is complete, the reaction mixture is maintained at -70 ° C for 0.5 hour, after which the mixture is allowed to warm to room temperature. The reaction mixture is poured into 500 ml of water. The mixture is acidified to pH 1 by addition of 1N hydrochloric acid. The product is extracted with ethyl 5 acetate (two extractions each with 150 ml of solvent).

The solution is dried over magnesium sulfate. It is concentrated under reduced pressure. The product is crystallized from 50 ml of ether. The precipitate is filtered. This gives 21 g (58% yield) of 3,5-diphenyl-5-methyldithiohydantoin as a yellow powder with a melting point of 157 ° C.

Example 8 Preparation of 3,5-diphenyl-5-methyl-2-thiohydantoin according to Method F 4.7 g (20 mmol) of ethyl (2-isothiocyanato-2-phenyl) -propionate are dissolved in 40 ml of xylene. 2.16 g (20 mmol) of phenylhydrazine are added thereto, after which the reaction mixture is heated under reflux for 4 hours. The reaction mixture is allowed to cool to ambient temperature whereby a light brown precipitate precipitates. The precipitate is filtered off, washed with 5 ml of diisopropyl ether and then dried in vacuo.

This gives 4.6 g (77% yield) of 3,5-diphenyl-5-methyl-2- * · ·. * ·· thiohydantoin as a light brown powder with a melting point of 164 ° C. .

• · · · · · · ··· · · ·

Example 9 • · · V: Preparation of 5-methyl-5-phenyl-3- (2-pyridylamino) -2-thiohydantoin according to Method F: -.- · · · · ·. Dissolve 2 g (9 mmol) of methyl (2-isothiocyanato-2-phenyl) -propionate in 30 ml of tetrahydrofuran. To it is added a solution of 0.99 g of 2-hydrazinopyridine in 10 ml of · · ·: ... * tetrahydrofuran. The temperature of the reaction mixture then rises to 20 ". * From 35 ° C to 30 ° C and the precipitate separates. The reaction mixture is allowed to react for 0.5 h at 30 ° C, then cooled to 5 ° C. A solution of 27 g of potassium tert-butylate in 10 ml of tetrahydrofuran is then added thereto, whereby the reaction mixture is colored violet. The reaction mixture is allowed to warm to room temperature and reacted for 2 hours. The reaction mixture is poured into 150 ml of water. 5 The mixture is neutralized with acetic acid. The product is extracted with 150 ml of ethyl acetate. The solution is washed with water, dried over magnesium sulfate and then treated with activated carbon. The solution is concentrated and the product is crystallized from 20 ml of diethyl ether. The precipitate is filtered off and dried in vacuo. 1.5 g (60% yield) of 5-methyl-5-phenyl-3- (2-pyridylamino) -2-thiohydantoin are obtained in the form of a pale yellow powder with a melting point of 80 ° C.

By this method, compounds of formula (VII), which are intermediates of compounds of formula (I), have been prepared and are listed in the following table, numbered starting with 1001.

B

20 R, ^ S

X Y

: ···: R 'VNNB, n-R4

*: 25 Oh

R 1 = methyl and R 2 is phenyl.

. 30 ♦ · • · · ♦ ♦ ♦ ♦ .. .. ... 35 • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · • • • • • • • pit • • • • • • • • • • • • • • • 28

Well. n B R 4 S-to. Sp.

1001 1 NH Ph 66% 164 ° C

1002 l NH roetatolyl 62% 174 ° C

5,1003 1 CH 2 Ph 46% 125 ° C

1004 1 NH paratolyl 13% 162 ° C

1005 1 CH 2 2-thienyl 49.5% 134 ° C

1006 1 NH 4 -FluoroPh 30% 162 ° C

1007 1 NH orthotolyl 38% 162 ° C

10 1008 0 -isopropyl 60.5% 146 ° C

1009 l NH 3 -chloro Ph 32% 78 ° C

1010 1 NH tert. -butyl 18% at 120 ° C

1011 1 NH 4 -chloroPh 24% 196 ° C

1012 1 NH 2 -chloroph Ph 69% 172 ° C

15 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

20 1018 1 NH 4 -NO 2 -Ph 41% 234 ° C

1019 1 NH 2 -Pyridyl 60% 80 ° C

1020 1 NH 3-pyridyl 17% 174 ° C

Example 10

Preparation of Compound 9 According to Method G 11.1 g (50 mmol) of methyl (2-isothiocyanato-2-phenyl) propionate are dissolved in 150 ml of anhydrous tetrahydrofuran.

'* • * 30 To this mixture, add gradually, over 10 minutes, a solution, «·. . ·. containing 5.4 g (50 mmol) of phenylhydrazine in 50 ml · · ·: ·. anhydrous tetrahydrofuran. The temperature of the reaction mixture rises to 3 · 5 ° C. At the end of the addition, the reaction mixture is reacted with · · · *! *! After 0.5 hours at 30 ° C, the reaction mixture is cooled to -5 ° C. At this temperature, a solution of 5.6 g (50 mmol) of potassium tert-butylate in 50 ml of anhydrous tetrahydrofuran is added. The reaction mixture ·· · ♦ V turns violet and a precipitate forms. The reaction mixture is allowed to react for 0.5 h at 0 ° C, followed by the addition of 8.5 g (60 mmol) of methylene chloride. iodide. The reaction mixture is allowed to react for 1 hour at room temperature. The reaction mixture is diluted with 200 mL of ethyl acetate. The reaction mixture is washed twice with 150 ml *: 1: water each time. The solution is dried over magnesium sulfate and then treated with activated carbon. The solution is concentrated to give a violet-brown honey-like substance which is crystallized from 50 ml of ether. The precipitate is washed and then dried under vacuum. A second crop of product is obtained by concentration of the mother liquor and stirring of the honey-like residue obtained in 50 ml of diisopropyl ether. This gives 12 g (77% yield) of 4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound 9) as a light brown powder, m.p. 149 ° C.

10 By following the procedure described above, the following compounds are obtained: R2x / NX / S “CH3 Ri O ^ r4 20 25 ································································· · · · · · · · 30 • · · • ♦ ♦ · 4 4 4 4 4 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 .1: 135 · · 1 1 • • • 1 1 1 1 1 1 1 1 1 1 1 1. * ···· ♦ ·· • · ♦ »··· jk c. 45 ·· · • «» • · • · »

G G

0) <D

G G

• H · Η

(Ö (O

g S

(0 (0 υ · ηυ · ι-ιυυυυυυυυυυ o (0 o cOoooooooooooooooooooooooo

G G

• lOGt- ^ GinaiconinHcoionniioootncoinricooiococo ^ vo 0 «Hgvogair ^ 'tfr ^ vDtnin ^ mr ^ vDnco ^' incoiot ^ C '^' t ^ vocje ·) CQ HE Z HHHHH HHHHHHHH HHHHHHHH

g Ή Ή Ή

fri H H G MH

CO> ι> ι> ί> i> i -> ι> ι Λ (¾> ι 0) Ό Ό I Λί ΙΌ g g g g g g g g g g

S Η Η Η CO Ρ-ι Ρ-ι CO · Η Ρ-ι Ρ-ι 1¾ Ρ-ι GM, iG GM GU GM O-ι CM

—'MM II I II IM III I I PM I I I I I

I> i> i GJ 0) <D <D 0)> 1 Hl ΦΗ HHIH <DH <D <D

H ftftO g gg gOi ggU UUMJgOgg _ - * »gllgglggllgllglllggllllllll« g COgnCOggCOggOCOgncSIgCOCJCOgg ^^^ n ^ COCOC ·).

C/O

C/O

g CO o

HM MMM HiM hrH MH Hpl HM WH HM hr · HM HM HM HM HM HM HM HM HM M HM HM hrl M hH

HM W HM HM HM HHHkHMHMHMHMHMHMHMHMHMHM HM HM HM HM HM HM HM HM HM HM

«·· n a ^ -uusgssssssssssssssasagggss • · • ·» ♦ • · · »« ·

fM

«· • * • · · t. cncocflcococnwcncncflcowwwwwwwwwwwwwcnwcflw

• · · <*> <D <D <D <D <D <D <D <D <D <D <D <D <D <D <D <D <D <D <D {D <D <D (D <D <D <D <D <D

«Gggggggggggggggggggggggggggg *% ♦ · · •« t ♦ «• 94 9 · ·

• · · CO CM CO

•

CM CM CM

ffi ffi ffi ... M ΦΦΦΦΦΦΦΦΦΦΦΦΦΦΦΦΦΦΟΟ ΦΦΦΦΟΦΦ: ·: «gggggggggggggggggggggggggggg • · ··» «· · · ·

• CO CO

Ψ.:. o o o co o <D M <D0) <DgMiHgg H rHHHi — liH H rl

... H g OggggUUUgCnU UOUUU UU

• · - Il I I I I g I I I I I I I I II

... g II II 1 ^ 1 ^ 11 ^^^^^^^^ 1 • <· il

·· · - - H

I * l en en g «· ♦

* * · COhiflhCOM'iin ^ hCOmOHfOM'J ^ hCOCIlOHiNn'JinvD

O lfi «hM ^ MMWCOCOCOCOOWM] \ mOU] \ 01 <Jl <iOOOOOOO

g HHHHHHH

tn o m o m o H H CO CO n υυυυυυυοοοοο Hnn H HnHcocoH ^^^ vor ^ cococnmt ^ orvjvo

Ot cNvo '^ vovocnr'COC'qcoininr'invooqcMHin

CQ HHHHHHHHHHHHHH rl H rl H

Λ (¾

I U

si <M> 1 CL, _____ Pli Ä ΙΛΛΧ3Χ3ΛΛ, C Λ Λ Λ 0) I α, ΛίΝ &, α, α, &, Λα, ίΐΛα, ΑΛείΝΛΛΛ I (¾ I I I I I I PL, I I I I —'I PU Ph P-,

Φ I I H H rH Φ rH «H I 0) 0) (1) H I H I I I ShinUUUSUUfeSSSO'iUfefeh. * · I I - I I I I I I I I I I - I I I I

p $ nncj ^ CM ^ fMnn ^^^ in ^ ojncMiNfM

hr <hr * tr * * t * hr * hr * hh hr * hr ** r> ** T4, THhr'hr4hr ^ h, H * iH, T1 | hh

HH HH HH HH HH HH HH MH HH HH HH HH HH HH HH l-H HH HH HH

... n ggsssssssssgsgssssg • · • · I «• · · • · · · · · · • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • tncncflcncnwcntococncowwcnoicntncnt / iin 0) (1) (1) (1) 0) (1) 0) (1) (1) (1) (1) (1) (1) 0) 0) (1) (1) (1):. :: e ggggggggggggggggggg • · • · · «· • · • · «

• · «CO CO

* «" * "« * #> "S

CM CN

DC DC

cm ΦΦΦΦΦΟΟΦΦΦΦΦΦΦΦΦΦΦΦ sv k ggggs — ggssssgsasss • · * ♦ »• · · • · · *: * 0) (1) 0) (1) 0) 0) ι-h a) * ::: h ^ gg gfegg ^ gh u ^ g

. . - I II I I I I I I I III

· ... · PO I 1 ^^ 1 1 ^^ - ^ * · «· • · ·« · r-ooaiOHcOMtfiovor ^ co ^ Hcqn ^ invo O OOOrlHHHHHHHHHfNMOIMCNO].

g rlrlrlrlHHHHHHHrlHHHHHrlH

LO O ID O LO O

H H {N {N {O

32

Example 11 Preparation of 4-Phenyl-4-methyl-1- (phenylthio) -2-methylthio-2-imidazolin-5-one (Compound 95, mp 112 ° C) In a 100 mL three neck flask, place under an inert atmosphere. , 6 g (2.7 mmol) of 2-methylthio-4-methyl-4-phenyl-2-imidazolin-5-one dissolved in 50 ml of anhydrous tetrahydrofuran (THF). The reaction mixture is magnetically stirred and cooled to 0 ° C (in an ice-acetone bath). 0.30 g (1 molar equivalent) of potassium tert-butylate are added thereto and the mixture is stirred for 10 minutes at 0 ° C. A solution of 0.40 g of phenylsulfenyl chloride in 10 ml of anhydrous THF is then added to the reaction mixture. The reaction mixture is allowed to warm to room temperature over one hour. The reaction mixture is poured into 100 ml of water. The mixture is extracted with 100 ml of ethyl acetate. The organic phase is washed 4 times with water and dried over sodium sulfate. The organic phase is concentrated in vacuo. This gives a yellow honey-like substance which is crystallized from isopropyl ether after purification on silica gel in 68% yield (melting point 112 ° C).

♦ · ·. *: Example 12 ♦ ·: In Vitro Assay This example examines the compounds of the invention. · [: diseases on cereals and other plants.

♦ · • · · • * * Fusarium oxvsporum F.sp. melon 30 Rhizoctonia solani AG4 ·· · “· Helminthosporium gramineum • · · ·. * * Pseudocercosporella herpotrichoides«.:. Alternaria alternata ····. ···. Septoria nodorum • · 35 Fusarium roseum ··· Pvthium rostratum ***** Pvthium vexans 33

In each experiment, the following procedure is used: medium containing potato, glucose and agar (PDA medium) sterilized in an autoclave at 120 ° C, is poured into petri dishes (100 ml / dish) and ice-5 is added. mettyä.

As the medium is poured onto the plates to solidify, an acetone solution of the active substance is added thereto to achieve the desired final concentration.

10

For comparison, petri dishes of the type described above, to which an equal volume of medium but no active ingredient is added, are used.

After 24 hours, each dish is inoculated with a chopped homemycel obtained from the culture of this mold.

The plates are kept for 5 days at 20 ° C, after which the growth of the mold on the plates containing the active substance to be tested is compared with the growth of this mold on a control plate.

For each test compound, its ability to inhibit mold growth at 20 ppm is determined.

25 * This gives the following results:

• M

:. ·. activity was found to be good, that is, mold growth inhibited by 80- • · *. 100%, in the case of the compounds I, 9, 13, 16, 22, 26 and 34 for molds Pvthium rostratum and Pvthium vexans, 30 for compound 26 Fusarium oxvsporum and Fusarium roseum in the case of compounds 11, 16, 22 and 26, molds of Alter mildew in the alternata, · · ·. - in the case of compounds 11, 16 and 26, mold Rhizoctonia · · * '* 35 per my sol, • · ·:.' for Pseudocerco * · '** sporella herootrichoides, for compounds 16 and 26, for Septoria nodorum for compounds 11, 16 and 26, for Helmin-thosporium arannneum for compounds 9, 11, 16 and 26.

5

Example 13

In vivo experiments on vine leaf Plasmopara Viti-cola 10 The active substance to be tested is finely ground in a water suspension having the following composition: - active substance 60 mg - surfactant Tween 80 0.3 ml (polyoxyethylene sorbitan oleate), diluted 10 water is added to make up to 60 ml.

This aqueous suspension is then diluted with water to achieve the desired concentration of active agent.

20

Seedlings of Chardonnay (Vitis vinifera) are grown in small pots. When plants are 2 months old • · ·; (having 8 to 10 leaves and 10 to 15 cm in height), they are treated by spraying with the aqueous suspension described above.

• · • «· • · · · · ·. ·. : The reference plants are treated by spraying with an aqueous solution, • · ·, 1 ./, which does not contain the active substance.

After drying for 24 to 24 hours, each plant is minced by spraying with water-borne Plasmopara viticola spores, obtained from a 4-5 day culture. a pension containing 100,000 spores / cm3.

The contaminated plants are then incubated for two days at about 18 ° C, in a humidified atmosphere, and then for 5 days. for 24 hours at 20-22 ° C in an atmosphere having a relative humidity of 90-100%.

Results are evaluated 7 days after contamination by comparison with control plants.

Under these conditions, it is noted that a concentration of 1 g / l of active agent provides good (at least 75%) or complete protection when the active agent is one of the following: 1, 2, 9, 10, 12, 13, 15 , 16, 18, 20, 22, 23, 24, 25, 30, 31, 34, 35, 37, 39-43, 45, 48, 55-58, 60, 62, 64, 68, 73, 75, 76 , 83-85, 88-91, 93-98, 101-108.

Example 14 15 In vivo test on wheat "rust mite" or Puccinia recondita mold

The active substance to be tested is finely divided by grinding an aqueous suspension having the following composition: 20 - active substance 60 mg surfactant Tween 80 0.3 ml (polyoxyethylene sorbitan oleate), 1 · [: diluted to 10% with water: to give 60 ml.

• · ·: ·. 25 • · 1:. ·. This aqueous suspension is then diluted with water to achieve the desired concentration of active ingredient.

Into pots containing a 50/50 µJO mixture of peat and pozzolanic soil, sown wheat, 10 cm high, is treated with • a · 1: 1 by spraying it with the aqueous suspension described above.

After 24 hours, the wheat is sprayed with an aqueous spore suspension, ···· · 1. containing 100,000 spores / cm. This suspension is obtained from contaminated plants. The wheat is then placed in an incubation cabinet for about 24 hours at about 20 ° C, with a relative humidity of 100%, followed by 7 to 14 days at 60% relative humidity.

The condition of the plants is evaluated at 8 and 15 days after contamination by comparing them to untreated control plants.

Under these conditions, it is noted that a concentration of 1 g / l of active agent provides good (at least 75%) or complete protection when the active agent is one of the following compounds: 2, 9, 10, 15, 18, 20-22 and 39, 55, 57, 64, 75, 83-85, 88-90, 93, 94, 98.

Example 15

In vivo assay on Phvtophthora infestans mold in tomato

The active substance to be tested is finely divided by grinding an aqueous suspension having the following composition: 60 mg 20 - surfactant Tween 80 0.3 ml (polyoxyethylene sorbitan oleate) diluted to 10% in water • · ·. water is added to obtain 60 ml.

This aqueous suspension is then diluted with water so that the desired concentration of the active substance is reached.

• · ♦ ♦ • · • · ♦ ♦ · · # ·; ·. Tomato plants (Marmande species) are grown in pots. When the plants are one month old (having 5-6 leaves ... .30 and 12-15 cm tall), they are treated by melting them with the aqueous suspension described above, where - *. * * concentration varies.

· # · ♦ ·· *. ** ·. After 24 hours, all plants are contaminated by digestion with an aqueous suspension of 30,000 spores of Phvtophthora infestans mold (30,000 spores / cm).

After this contamination, the tomato plants are incubated for 7 days at a temperature of about 20 ° C in a humidified atmosphere.

5 At 7 days after contamination, the results obtained with the plants treated with the active substance to be tested are compared with those obtained with the reference plants. Under these conditions, it is noted that a concentration of 1 g / l of active agent provides good (at least 75%) 10 or complete protection when the active agent is one of the following: 2, 9, 15, 30, 39, 45, 55 , 68, 75, 84, 85, 90, 98, 107, 108.

These results clearly show that the derivatives of the invention have good fungicidal properties in a wide variety of genera such as Phvto-mvcetes. Basidiomvcetes. Ascomvcetes. Adelomvcetes it Funai imperfecti. fungi and mold, in particular vine plants, vine plants, tomato plants and rust in wheat.

* · ·; In practice, the compounds of the invention are rarely used: alone. In most cases, these compounds are included in the compositions. These compositions, which may be used in fungi:. as binders, containing as active ingredient kekek · · ·, ·. ; a compound of the invention as described above in admixture with solid or liquid carriers acceptable in plant cultures and surfactants which are likewise approved in plant cultures. In particular, conventional inert carriers and conventional surfactants are useful. The invention also relates to these compositions.

«• I • · · ·. ···. These compositions may also contain any other ingredients, such as protective colloids, binders, packing, thixotropic agents, penetration enhancers, stabilizing agents, chelating agents. substances and 38 others. More generally, the compounds of the present invention may be used in combination with any solid or liquid excipients which are consistent with conventional techniques for the preparation of such compositions.

In general, the compounds of the invention will usually contain from about 0.05% to about 95% by weight of a compound of the invention (hereinafter referred to as an active agent), one or more solid or liquid carriers, and optionally one or more surfactants.

As used herein, the term "carrier" refers to an organic or inorganic, natural or synthetic substance to which a compound is combined to facilitate its application to plants, seeds or soil. Thus, this carrier is generally inert and must be acceptable in crop production, especially in the treated crop. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fats and the like) or liquid (water, alcohol, especially butanol and the like).

• · · • • • • •. The surfactant may be ionic or nonionic, emulsifying, dispersing or wetting agents, or the like; a mixture of active substances. Examples include • · · * Γ | salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic acids, · · · polycondensation products of ethylene oxide with fatty alcohols, fatty acids or fatty amines, especially substituted phenols (or phenols). arylphenols), salts of sulpho esters, succinic esters, taurine derivatives (especially alkyl taurates), phosphoric esters of polyoxyethylated alcohols or] *** # phenols, esters of fatty acids and polyols, of the above -, sulpho · · ·: derivatives of the functions of sodium and phosphate. Generally, it is necessary that at least one surfactant 39 be present if the compound and / or inert carrier is not soluble in water and if water is used as a vehicle.

Thus, the crop compositions of the invention may contain the active compounds of the invention in very different amounts, ranging from 0.05% to 95% by weight. They preferably contain from 5 to 40% by weight of surfactant.

These compositions of the invention, in turn, are in a wide variety of solid or liquid applications.

Forms of use of solid compositions may include dusts suitable for dusting (in which the concentration of the compound may be up to 100%) and granules, especially granules obtained by extrusion, compression, impregnation of a granular carrier, granulation of powder (in the latter case , 5-80%), compresses or effervescent tablets.

20

The compounds of formula (I) may also be used as a dusting powder; whereas the composition may also be used;. comprising 50 g of active ingredient and 950 g of talc; likewise:: *; a composition comprising 20 g of active ingredient, 10 g of fine silica and 970 g of talc may be used; compo •:. ·. The nents are mixed and ground and the mixture is applied by dusting.

For liquid compositions or uses intended to be converted into liquid compositions prior to use, solutions, particularly water-soluble concentrates, may be mentioned. · *. * * Emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or dustable powders), pastes, gels. Emulsifiable or soluble concentrates usually contain 10-80% active ingredient, while ready-to-use emulsions or * * · ** · concentrates contain 0.001-20% active ingredient. agent.

40

In addition to the solvent, the emulsifiable concentrates may contain from 2% to 20%, if necessary, of additives such as stabilizers, surfactants, penetration enhancers, corrosion inhibitors, colorants or the aforementioned additives.

These concentrates can be obtained by diluting emulsions with water, which may have any desired concentration particularly suitable for plant cultures.

10

The following are examples of the composition of some emulsifiable concentrates:

Example ET1 15 - active ingredient 400 g / l - alkaline dodecylbenzenesulfonate 24 g / l 20 - nonylphenol oxyethylated with 16 g / l 10 molecules of ethylene oxide - cyclohexanone 200 g / l 25 - aromatic solvent to give a total volume of 1 liter.

According to the instructions for the manufacture of another emulsifiable concentrate, e e ϊ *** 30 is used as follows:

Example ET 2 · · - active substance 250 g e 35 - epoxidized vegetable oil 25 g • e · e · · · · · 1 - mixture of alkoylaryl sulfonate and polyglycol ether and fatty alcohols 100 g -40 «***; - dimethylformamide 50 g • 1 · · · · · - xylene 575 g.

Concentrated suspensions, which are also applied by spraying, are prepared to provide a flowable, stable product, the components of which do not separate, and usually contain from 10% to 75% active ingredient, 0.5% to 15% surfactant. active ingredients, 0.1-10% 5 thixotropic agents, 0-10% suitable additives such as antifoam, corrosion inhibitor, stabilizing agents, penetration enhancers and binders, and as a carrier water or organic liquid with low or no active material not soluble at all. Certain solids or mineral salts may be dissolved in carrier 10 to prevent component settling or water bubbling.

The following is an example of a concentrated suspension.

15

Example vsi - active substance 500 g - polyethoxylated tristyrylphenol phosphate 50 g - polyethoxylated alkylphenol 50 g 20 - sodium polycarboxylate 20 g - ethylene glycol 50 g - organic polysiloxane oil 1 g Γ **: (antifoam agent) i · polysaccharide · . 25 - water 316.5 g • · • # t • · ·

Wettable powders (or dustable powders) are usually formulated to contain from 20% to 95% of the active ingredient and usually contain from 0% to 30% of the wetting agent in addition to the solid carrier 3. -20% dispersant and, where appropriate, i. * 0.1-10% one or more stabilizers and / or other auxiliary substances, such as penetration enhancers, binders, ... anti-caking agents, colorants and the like. - · «··, ···. via.

In order to obtain dustable powders or wettable powders, the active ingredient is mixed thoroughly in suitable blenders with other components of the powder, followed by grinding in mills or other suitable grinding equipment. In this way, dustable powders are obtained which can be moistened and suspended in a favorable manner. These powders can be suspended in water at any desired concentration and these suspensions can be used very advantageously, for example, for application to plant leaves.

Instead of wettable powders, pastes can be made. For the pastes 10, the manufacturing conditions and procedures are similar to those for wettable powders or dustable powders.

The following are examples of different compositions of wettable powders (or dustable powders):

Example KJ1 - active ingredient 50% - ethoxylated fatty alcohol (wetting agent) 2.5% 20 - ethoxylated phenylethylphenol (dispersant) 5% - chalk (inert carrier) 42.5%! ** ': Example KJ2 • · •: 'j - active substance 10% i \ 25 • 1 ·· - branched synthetic C13-oxo alcohol, 0.75 S. ·, ethoxylated with 8-10 ethylene oxide (wetting agent) • «· ♦ e · · i - s - neutral calcium lignosulfonate 12 % ^ .. 130 (dispersant) e «· - calcium carbonate (inert filler) so as to obtain 100% · · · · · 35 · Example KJ3 This wettable powder contains the same ingredient as in the previous pre- ···· in the label, however, in the following proportions: • te ·· · · · · «t: .140» 43 - active substance 75% - wetting agent 1.50% - dispersing agent 8% - calcium carbonate (inert filler) 5 to obtain 100%

Example KJ4 - active ingredient 90% - ethoxylated fatty alcohol (wetting agent) 4% 10 - ethoxylated phenylethylphenol (dispersant) 6%

Example KJ5 - 50% active agent - mixture of anionic and nonionic surfactants (wetting agent) 2.5% - sodium lignosulfonate (dispersant) 5% - kaolin clay (inert carrier) 42.5%

Aqueous dispersions and emulsions, for example those compositions obtained by diluting with water the wettable powder or emulsifiable concentrate of the invention, are generally within the scope of the present invention. The emulsions may be water in oil or in oil. ·: In water type and may have a thick consistency, pre: · *: signifying "mayonnaise".

• · ·: · .25 • · ·:. ·. The compounds of the invention can be made into water-dispersible granules, which are also within the scope of the invention.

These dispersible granules, which generally have a bulk density in the range of about 0.3 to about 0.6, have a particle size generally in the range of about 150 to about 2000, preferably about 300-1500 microns.

These granules generally contain from about 1% to about 90% of the active ingredient, · · ·. preferably 25-90%.

• · • · · • 35 «· · • i ·:. ' The remainder of these granules consists essentially of a solid filler and optionally surfactant excipients 44 which impart the property of dispersing the granules in water. These granules can be of essentially two types depending on whether or not the retaining filler is soluble in water. When the filler is soluble in water, it may be inorganic or preferably organic. Excellent results have been obtained with urea. The water-insoluble filler is preferably an inorganic material, for example kaolin or Bento-rivets. Surfactants (2 to 20% by weight of the granules) of which at least one dispersant, essentially an anionic dispersant such as an alkali or alkaline earth metal polynaphthalene sulfonate or an alkali or alkaline earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as alkali or alkaline earth alkoyl-15 naphthalenesulfonate.

Other excipients such as an antifoam agent may also be added to the filler, but this is not necessary.

The granules of the invention may be prepared by mixing the ingredients necessary for making the granules by a variety of techniques known per se (granulating device, fluidized bed, nozzle, extrusion, and the like). The granulation is usually terminated by grinding, after which the granules are screened to obtain a particle size above:. areas.

The granules are preferably prepared by extrusion, as described in the following examples.

.. .30 • · · · · * Example DR1 ··· • · · * · * * Dispersible Granules * ♦ · ♦ ·· ··

90% by weight of active substance and 10% ··· #e \ 35 urea beads are mixed in the mixer. The resulting mixture is then comminuted in a barbed roll mill.

This gives a powder which is moistened with about 8% by weight of water. The wetted powder is extruded by means of an extruder having a perforated cylinder. The resulting granules are dried, crushed and screened to obtain granules having a particle size in the range of 15 to 2000 microns.

5 Example DR2

The following components are mixed in the mixer: - 75% active ingredient - wetting agent (sodium alkylnaphthalene sulfonate) 2% - dispersant (sodium polynaphthalene sulfonate) 8% 10 - water insoluble inert filler (kaolin) 15% This mixture is granulated in a fluidized bed and so as to obtain granules having a particle size in the range of 0.15 to 15.80 mm.

These granules can be used alone, in the form of an aqueous solution or dispersion, which has been made to achieve the desired dosage. They can also be used to prepare mixtures containing other active substances, in particular fungicides, whereby these fungicides are in the form of wettable powders or granules or aqueous suspensions.

• · · · · · · ·

Storage and transport resistant compositions contain: 1 to 25% by weight of the active ingredient, preferably 0.5 to 95% by weight.

The invention also relates to the use of the compounds of the invention for the control of plant, fungal and mold diseases by treating plants or a site thereof for the prevention or treatment of these diseases. .

• · · • • • • · ** | They are preferably applied at a rate of 0.005-5 ··· kg / ha, more particularly 0.01-1 kg / ha.

···· • 1 · • 1 • · «· · * 35 • · · • · · •» · 46 Jan. A — R, V 7 r / Vn. (I) 1 f X (B) n -R 4

W

«W« 1 VnTSR3 rvn ^ sr =

'' VsJU - Rl / T * 4 »W

w ^ w R3 W li lb 'R2yVSCH3 R2yN * YSR3

R 1 / 'N "(B) n-R 4 R f r N" (B) n-R 4 0 0 ac) Id "0 S .sch 3 VY' SCH 3 R / VNSm.

Ri Y '' (BJn-R * Ri C ° 2H

W ^.

0Π) (Π) • ft ft ft · • · * * * * * * * *>>

:. ·. K S

: SCH R'X / N "^ H

••• 00 W °: *: (VH) • · · • · · 9 · * \ r2 * ::: ri-c-n = c = s \ ·: co2r: ·: ·. <M.

• · • ·

Claims (35)

Compounds having imidazolinone or imidazoleintion group, characterized in that they have the following general formula (I): r2v n ^^ a-r3 XX H (B) n-R4 W (I) in which: 15. W is a sulfur atom or oxygen atom or the group S = 0, - A is 0 or S, - n = 0 or 1 - B is N (R5) or 0 or S or C (R5) (R6) or SO2 or: * · *: C = 0; • · 20. R 2 and R 2, identical or different, represent: • · · • · • · • · · m: - H, provided that one of the 2 groups is not H, or • · · [Γ J - an alkyl or haloalkyl radical of 1-6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalyl, alkylaminoalkyl 1-, alkenyl or alkynyl radical of 2-6 carbon atoms, or • : - a dialkylaminoalkyl or cycloalkyl radical of 3-7 carbon atoms, or - an aryl radical containing phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or •. methylenedioxyphenyl, optionally substituted with 1-3 groups of R ,, or R • an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, where the terms aryl and alkyl have the definitions given above, or - R 1 and R 2 together with the carbon to which they are bonded in the ring may form a carbocycle or a heterocycle of 5-7 atoms, which rings may be fused with a phenyl optionally substituted with 1-3 groups selected from R 7 ; - R 3 represents: - an alkyl group of 1-6 carbon atoms, or - an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group of 2-6 carbon atoms, or 15. a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group of 3-6 carbon atoms, or - an N, N-dialkylcarbamoylalkyl group of 4-8 carbon atoms, or - an arylalkyl group wherein the alkyl moiety is a radical of 1-6 carbon atoms and the aryl moiety is phenyl, naphthyl, thienyl, furyl or pyridyl, optionally substituted with 1-3 groups selected from ·· · P *. , * -TS-7 / • · [I - R4 represents: • · · · · · • · • · * * - a hydrogen atom when n is equal to 1, or • · ·: - an alkyl group of 1-6 carbon atoms, or • · · *. "- an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group of 2-6 carbon, or in: *: - a dialkylaminoalkyl, alkoxycarbonylalkyl, or N- • · · ·; ***; alkylcarbamoylalkyl group having 3-6 carbon atoms, or • · · *. - an N, N-dialkylcarbamoylalkyl group of 4-8 carbon atoms, or - an aryl radical containing phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzo- • · ·; furyl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted with 1-3 groups selected from R7, or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radical, where the terms aryl and alkyl have the above definitions, and - amino group, disubstituted by two identical or different groups selected from: - an alkyl radical of 1-6 carbon atoms, - an alkoxyalkyl, alkenyl or alkynyl radical of 3-6 carbon atoms, - a cycloalkyl radical of 3-7 carbon atoms, 10. an arylalkyl radical , as defined above, a phenyl or naphthyl radical, optionally substituted with 1-3 groups selected from R 7 or - a thienylmethyl or furfuryl radical, or R 4 represents: 15. a pyrrolidino, piperidino, morpholino or piperazine radical; group, optionally substituted with alkyl of 1-3 carbon atoms; - R5 represents: - H, except when R4 is H, or - an alkyl, haloalkyl, alkylsulfonyl, or haloalkylsulfonyl radical of 1-6 carbon atoms, or - an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxy, alkylsulfonyl, or cyanoalkylsulfonyl radicals having 2-6 carbon atoms, or more. - an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or 3-6 carbon atoms cyanoalkoxycarbonyl radical, or the formyl radical, or a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical of 3-6 carbon atoms, or M · I: 3: - a cycloalkylcarbonyl radical of 4-8 carbon atoms, or a phenyl radical; arylalkylcarbonyl, especially phenylacid. tyl and phenyl propionyl radical; arylcarbonyl, especially benzyl radical, optionally substituted with 1-3 groups selected from 2 · 3 ί ^ ϊ! R7; tienylkarbonyl-; furylkarbonyl-; pyridylkarbonyl-; benzy · · · · loxycarbonyl; furfuryloxikarbonyl-; tetrahydrofurfuryloxycarbonyl-; tienylmetoxikarbonyl-; pyridylmetoxikarbonyl-; phenoxycarbonyl or phenylthiol carbonyl radical, wherein the phenyl itself is optionally substituted with 1-3 groups selected from R al kyltiolkarbonyl-; haloalkyltiolkarbonyl-; alkoxialkyltiolkarbo-alkyloxycarbonyl; cyanoalkyltiolkarbonyl-; bensyltiolkarbonyl-; furfuryltiolkarbonyl-; tetrahydrofurfurylthiolcarbonyl-5; thienylmethylthiolcarbonyl-; pyridylmethylthiolcarbonyl or arylsulfonyl radical, or - a carbamoyl radical, optionally mono- or disubstituted by - an alkyl or haloalkyl group of 1-6 carbon atoms, or - a cycloalkyl, alkenyl or alkynyl group of 3-6 carbon atoms, or - a alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2-6 carbon atoms, or 15. a phenyl optionally substituted by 1-3 groups R7 'or R5 represents: - a sulfamoyl group, optionally mono- or disubstituted by 20. or a haloalkyl group having 1-6 carbon atoms, or - a cycloalkyl, alkenyl or alkynyl group having from 3-6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group. with 2-6 carbon atoms, or • · · ··· · - a phenyl optionally substituted by 1-3 • · · · · · · 1: groups R7; · · · · · · or R5 represents: with 3-8 carbon atoms or: cycloalkylsulfony l group of 3-7 carbon atoms; ··· · • · · «· • · • · · *. - R6 represents: - a water atom or - the cyano group or 35. an alkyl group of 1-6 carbon atoms or a cycloalkyl group • • ••• I of 3-7 carbon atoms or • · - an acyl or alkoxycarbonyl group of 2-6 carbon atoms or - the benzoyl group, optionally substituted by 1-3 groups R 1; - R 7 represents: 5. a hydrogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical of 1-6 carbon atoms or - a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy alkenylthio or alkynylthio radical of 3-6 carbon atoms or - the nitro or cyano group or - an amino radical optionally mono- or disubstituted by an alkyl or acyl radical of 1-6 carbon atoms or alkoxycarbonyl of 2-6 carbon atoms; 15. a phenyl, phenoxy or pyridyloxy radical, which radicals are optionally substituted; and their salt forms, except for compounds for which, when R 2 and R 2 are simultaneously phenyl or simultaneously methyl, B is C (R 5) (R 5), A is sulfur and W is 0 or S; With the exception of the three compounds with R = hydrogen, n = 1, B = • · ·] · * · * NR5, with R5 and R4 = methyl, AR3 = SCH3, W = O and R 2 are either a hydrogen, a methyl or a phenyl; **: except for the compound in which Rx is a phenyl, R2, R3 and • · ·: R4 is methyl, n is equal to noil, and A and W each is a sulfur atom; . *. * · 3 0 • · · • · · ·. ·· *. likewise except for the compounds of formula (I) in which: • · • - n = 0; and - Rx and R2 simultaneously represent a methyl; and '*** · - A is a sulfur atom; and J*. - R 4 is a phenyl substituted by two groups: the one selected from the groups cyano, nitro or a halo genome; - the second selected from a group of trifluoromethyl or a halogen atom; and except for the following compounds: - 3 - [(4-chlorophenyl) sulfonyl] -3,5-dihydro-2-methoxy-5-methyl-5 (1methylethyl) -4H-imidazol-4-one; - 2- (ethoxycarbonylmethylthio) -3-acetyl-5,5-diphenyl-3,5-dihydro-4H-imidazol-4-one; - 2-butoxy-5-ethyl-3,5-dihydro-3-methyl-5-phenyl-4H-imidazol-4-one; 10-2-methoxy-5-methyl-3,5-dihydro-3- (1-phenylethyl) -4H-imidazol-4-one; - 2- (methylthio) -5,5-dimethyl-3,5-dihydro-3-phenyl-4H-imidazol-4-one; - 2- (methylthio) -3,5,5-triphenyl-3,5-dihydro-4H-imidazol-4-one; 3-methyl-2- (methylthio) -1,3-diazaspiro [4,5] dec-1-en-4-one; - 3-methyl-2- (methylthio) -1,3-diazaspiro [4,5] dec-1-en-4-one. Compounds according to claim 1, characterized in that A is a sulfur atom. Compounds according to claim 1, characterized in that W is an oxygen atom. • · · ··· • · • · *. Compounds according to claim 2, characterized in that they correspond to the general formula: • ♦ • · · • ♦ ♦ ♦ · ♦ id v / SRi ♦ · · J 2 \ / f> c) h-r4 ··· * w I ·: * ♦: Re da) ·: * ·: 30 • · • · · * · * · 'in which W, n, R 2 -Rg have the same meaning as in claim 1 . • · Compounds according to claim 2, characterized in that they correspond to the general formula: r2v SR3 "" represents "Ks (lb) 5 in which W, R 2 R 1 has the same meaning as in claim 1. Compounds according to claim 2, characterized in that they correspond to the general formula: R2v XX H (B) n-R 40 dc). In which B, n, has the same meaning as in claim 1. 7. Compounds according to claim 2, characterized in that they correspond to the general formula: • ♦ • ♦ · '• r: * xx H (B) n-R4: o (id) • ·· • · • A compound having the same meaning as in claim 1. Compounds according to any one of claims 1-7, characterized in that R5 is a hydrogen atom. • · Compounds according to claim 5, characterized in that R 5 is a hydrogen atom (compound Ib '). Compounds according to any one of claims 1-3, characterized in that R 1 and R 2 are different from the hydrogen atom. Compounds according to any one of claims 1-10, characterized in that R 2 is an alkyl group having 1-3 carbon atoms. Compounds according to any one of claims 1 to 11, characterized in that Rt is a phenyl, optionally substituted with a group R,. Compounds according to one of claims 1 to 12, characterized in that R 3 is an alkyl group having 1-3 carbon atoms. 15 Compounds according to one of Claims 1 to 13, characterized in that R 4 is a phenyl, optionally substituted with a 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 (process A) of compounds of formula (I) according to claim 2, characterized in that an S-alkylation of 2-thiohydantoins of formula (II) is carried out. with a • · | A compound of formula R3X in the presence of base and solvent according to the scheme: • ♦ • ♦ »♦ ·· H: Σ: Ro N \ \ / Base • ^ + R3X ——— ————— - ^ (j) hi ί Ri Solvents e.g. (B) n-R4 ♦. in which formulas R2, R2, R3, R4, B, n and W have the same meaning as in claims 1 and X, the atom is chlorine, bromine, iodine or sul -kate group or an alkylsulfonyloxy or arylsulfonyloxy group. A process for the preparation of 2-methylthio-2-imidazoline-5-one compounds of formula (Ie) (process B) according to claim 6, characterized in that by cycling by simple heating in an aromatic solvent upon reflux, a compound of formula ( V) according to the scheme: 10 sch3 r2 n = c 'r2. V Να., Δ ....... „N / 7 A ./yx R 1, C-NH- (B) n-R 4 j 2 - (B) n-R 4 o (V) (IC) Wherein R 1 (R 2, R 4, B and n have the same meaning as in Claim 1. ... 18. Process for the preparation of compounds of formula (V) (process B) according to Claim 17, characterized in that a condensation of an iminodithiocarbonate of formula • t · 5 ** (lii) is carried out with an amine or a hydrazine of formula (IV) according to the scheme: • · • · · .sch3 sch3 V: R2 N = cA R2 n = c ^ v / SCH3 R4- (B) n-NH2 New /; sch3 i.: ': Av) / \: · * ·. Rl C09H .......... Rl .C-NH- (B) n-R4 ·: * // ....: 25 o • · ....: (m) (V) • 30. which: R2, R2, R4 have the same meaning as in, claim 1, • · n is equal to 1 and B represents NRS, R. has the same meaning as in claim 1; and the acid (III) is activated for this condensation in the form of acid chloride, dicyclohexylisourea by means of dicyclohexylcarbodiimide or imidazolid by carbonyldiimidazole. A process for the preparation of compounds of formula (Ib) (process Cl), according to the scheme: R2v Base R2s. Solvent \ Yv 'M ...........' "Γγ" w I W I 10. Rs Ib 'Ib characterized in reacting in a solvent in the presence of base a compound of formula R5X with a compound of formula (Ib) according to claim 5, wherein the group R5 is a hydrogen atom according to claim 9 (compound Ib' )), the groups R1-R1 have the meaning as defined in claim 1, the group R5 is an alkyl, alkoxycarbonyl, acyl, aroyl, alkylsulfonyl, arylsulfonylcarbamoyl- Or X represents a leaving group as a halogen, a sulfate group, a phenoxy, optionally substituted, or the group R 50 when R 5 is acyl, or an alkylsulfonyloxy group. Or arylsulfonyloxy group or a non-leaving group such as isocyanate or isothiocyanate. • · 25 «· · 20. Process for the preparation of compounds of formula (Id):. (Process C2) according to the scheme: • · · ··· · • Solvent • • • s> <+ R2x ^ ·: ··: Ri V ^ N \ Kl V ^ N \ (IB) n-R4 H (B) n-R 4 0 · 30 *: id · id characterized by reacting a compound of formula (Id) according to claim 7, wherein R 2 is a hydrogen atom (compound (Id ')) having a compound of formula R X in a solvent and in the presence of a base at a temperature between -30 ° C and 5 + 80 ° C, in which formula X is a chlorine, bromine or iodine atom and R has the same meaning as in claim 1. 21. Process according to claim 20, characterized in that the base is selected from the group containing an alcoholate, a metal hydride or an amide and the solvent is selected from the group containing ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide and aromatic solvents. Process for the preparation of compounds of formula (I) (process D) according to claim 1, in which W represents the group S = 0, characterized in that an S-oxidation of a compound of formula (I) is carried out in which W is a sulfur atom in which oxidation of 2-imidazoline-5-ions is carried out with a stoichiometric quantity of peroxides in a solvent at a temperature between -20 ° C and + 20 ° C. The process according to claim 22, characterized in that the peroxide is a peracid and the solvent is selected from the group comprising chloroform and methylene chloride. Compounds useful especially as intermediates in the preparation of compounds according to claims 1-15, characterized in that they correspond to formulas Ha, III, V and Vila: H:. I / SCH3 Y ^ sch3 ·: ··: f! n-r4 Ri co2h w I * * * TD ·. ·. · 30 K5 Ila III / SCH3 r, γ- <, „, XT κ / \ - ΝΗ- (Β) η-κ4 1 V" Xf-R * (V) (Vila) in which: - W, Rx R2, R4 and R5, n and B are as defined in claim 1, R4 is separated from hydrogen atom, except for compounds of formula IIa having: - W = S, - R2 = methyl, R2 = phenyl, R3 = hydrogen and R4 = methyl or phenyl; W = S, 15. R 3 = ethyl, R 2 = phenyl, R 4 = methyl and R 5 = hydrogen; and w = s, - R 3 = methyl, R 2 = p-tolyl and R 4 = methyl; R5 = hydrogen or methyl or R4 = phenyl, R5 = hydrogen; W = S; ..... - R 7 and R 2 = phenyl, R 4 = methyl and R 5 = H, except for the compounds of formula Vila with: • · j "- R 4 = methyl , R5 = methyl, R7 = hydrogen and R2 = methyl or::: phenyl. ·: · · · · · · · · · · · ·:.: 25. Compounds according to claim 24, characterized in that R5 is a hydrogen atom , R 2 represents an alkyl group of 1-3 carbon atoms, R 2 represents phenyl nucleus, optionally substituted with R 7, R • M ·. * ··. Represents phenyl nucleus optionally substituted with R 7. ··· 26. Compounds according to claim 24 or 25, characterized by * * that they correspond to the formula (Vila) .... 27. Compounds according to claims 25 or 26, characterized in that R2 represents methyl group. 28. Compounds according to claim 25, 26 or 27, characterized in that Rx represents phenyl nucleus. 29. Process for Preparation of 2-Thiohydantoins of Formula 5 (VII) (Process F): H t? Characterized by reacting a compound of formula (IV) R4 (B) nNH2 with isocyanates derived from amino acids of formula (VIII) prior to cyclization: r2 R, -CN = C = S <VIII) 2 0 | C02R • · • · A process according to claim 31, characterized in that the base is selected from the group containing an alkali alcoholate, an alkali hydroxide or a tertiary amine and the solvent is selected from the group containing ethers, cyclic ethers, alcohols, esters, DMF and DMSO. 33. Process (process G) according to claims 29 and 31, characterized in that before neutralizing the 2-thiohydrantoin derivatives by neutralizing the acidic environment, an alkyl halide R3X is used to form the compound of formula Id, where X is a chlorine, bromine or iodine atom or an alkylsulfonyloxy or arylsulfonyloxy group and R3 has the same meaning as in claim 1. 34. Fungicidal compositions comprising in association with one or more solid or liquid carriers acceptable in agriculture and / or surfactants as well as in agriculture a (or more) active material which is a compound of formula I as defined in any of the claims 1-15. 20 The fungicidal compositions of claim 34, characterized in that they contain 0.5-95% by weight of compounds according to any one of claims 1 to 15. 36. Fungicidal compositions according to claim 34 or 35, characterized in that they contain combinations of a compound. of formula I with another active material. · · · · · · · · · · · 37. Compositions according to claim 36, characterized in that the other active material is a fungicide. 38. Compositions according to Claim 36 or 37, characterized in that they can be obtained as granules which comprise a compound of formula In and wettable powders, granules or aqueous suspensions containing the other active material. * · · · · 39. Compositions according to claim 38, characterized in that the second active material is a fungicide. • · A method of treating crops that are affected by or prone to fungal or mold diseases, characterized in that preventive or therapeutic application of an effective amount of a compound according to any one of claims 1 to 15 or a composition according to claim 1 is applied. 34-39. Method for treatment according to claim 40, characterized in that the effective dose is between 0.005 and 5 kg / ha. 42. The method of treatment according to claim 41, characterized in that the effective dose is between 0.01 and 1 kg / ha. ·· · · · · · · · · · · ♦ ♦ · · ·· · · · · · · · · · · ♦ ♦ • · · ··· · • 1 • ♦ · • · ♦ • 1 • · · · · · · · · · · · · · · · · ··· · · · · · · · · · · · · · · · · · · · · · · ·