SK161494A3 - 2-imidazoline-5-one and 2-imidazoline-5-thione derivatives, method of their preparation and fungicidal composition containing these derivatives - Google Patents

Abstract

2-imidazoline-5-one or 2-imidazoline-5-thione derivatives have general formula (I) in which W is the sulphur or oxygen atom, or the group S=O, n is 0 or 1, A is N(R5) or O or S or C(R5)(R6) or SO2 or C=O, R1 to R4 are hydrogen or a hydrocarbon radical, optionally substituted by halogen atoms in particular. Used as fungicides in agriculture.

Description

2-Imidazolin-5-one and 2-imidazolin-5-thione derivatives, process for their preparation and fungicidal compositions containing these derivatives

Technical field

The invention relates to novel imidazolinone or imidazolinethione compounds which are useful for plant protection. The invention also relates to a process for the preparation of said compounds and products which may optionally be used as intermediates in said processes for the preparation of said compounds. The invention further relates to the use of said compounds as fungicides, to fungicidal compositions based on said compounds and to methods of controlling fungal crop diseases by using said compounds.

It is an object of the present invention to provide compounds having superior properties in the control of fungal crops diseases.

It is a further object of the invention to provide compounds that also have an improved application spectrum in the control of fungal crops diseases.

It has now been found that these objectives can be achieved using the novel compounds of the invention.

SUMMARY OF THE INVENTION

The present invention provides 2-imidazolinone or 2-imidazoline-5-thione derivatives of formula (I)

R (I) (A) n

in which

W is S or O or S = O, n is 0 or 1,

A is NR _g or O or S or CR _with R _e or SO ₂ or C = O,

R and R, 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 an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl or alkenylalkyl group; (C 2 -C 6) or (C 3 -C 7) dialkylaminoalkyl or cycloalkyl or aryl group comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, or isoquinolyl the phenyl groups are optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group, the aryl and alkyl radicals having the meanings given above, or

R 1 and R 2 together with the oxygen atom to which they are attached to the ring may form a carbocyclic or heterocyclic group containing 5 to 7 atoms, which rings may be fused to a phenyl ring optionally substituted with 1 to 3 groups selected from the meanings indicated for R .

R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms or a (N) -alkyloxycarbamoyl or alkoxyalkyl group; 6 atoms, carbon or

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

R represents a hydrogen atom when n is equal to 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 dialkylaminoalkyl, dialkylaminoalkyl, (C 3 -C 6) alkylcarbamoylalkyl;

N, N-dialkylcarbamoylalkyl of 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyridiminyl, pyrimidinyl a benzothenyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl group and optionally substituted with 1 to 3 groups selected from the meanings indicated for R? or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group, wherein the aryl and alkyl radicals have the meanings given above, or an amino group which is disubstituted by 2 of the same or different groups selected from the group consisting of

- (C1-C6) -alkyl,

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

- a cycloalkyl group containing 3 to 7 carbon atoms,

- arylalkyl, phenyl or naphthyl as defined above optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? or

- a thienylmethyl group or a furfuryl group of a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted with an alkyl group having 1 to 3 carbon atoms,

R is hydrogen when R _{4 is} not hydrogen, or alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl of 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynylcarbonyl, alkoxycarbonyl, haloacetyl, haloacetyl, haloacyl, having 2 to 6 carbon atoms or alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl having 3 to 6 carbon atoms or a formyl or cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or 6alkynylcarbonyl or alkynylcarbonyl group or a phenyl group, an arylalkylcarbonyl group, in particular a phenylacetyl group and a phenylpropionyl group, an arylcarbonyl group, in particular benzoyl optionally substituted with 1 to 3 groups selected from R, thienylcarbonyl, furylcarbonyl, pyridylcarbonyl, benzyloxycarbonyl, furfuryloxycarbonyl, tetrahydrofurfuryloxycarbonyl, thienylmethoxycarbonyl, phenyloxycarbonyl, phenyloxycarbonyl, phenyloxycarbonyl, phenyloxycarbonyl, phenyloxycarbonyl, phenyloxycarbonyl, the phenyl group itself is optionally substituted with 1 to 3 groups selected from R, (alkylthio) carbonyl, (haloalkylthio) carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl, (furfurythio) ) carbonyl, (tetrahydrofurfurythio) carbonyl, (thienylmethylthio) carbonyl, (pyridylmethylthio) carbonyl or arylsulfonyl or carbamoyl, optionally mono- or disubstituted

an alkyl or haloalkyl group containing 1 to 6 carbon atoms, or

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

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

a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R, a sulfamoyl group, optionally mono- or disubstituted

an alkyl or haloalkyl group containing 1 to 6 carbon atoms, or

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

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

a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? , (C 3 -C 8) alkylthioalkylsulfonyl or (C 3 -C 7) cycloalkylsulfonyl group,

R is 6 hydrogen or cyano or C 1 -C 6 alkyl or C 3 -C 7 cycloalkyl or C 2 -C 6 acyl or alkoxycarbonyl or benzoyl optionally substituted with 1 to 3 groups selected from the meanings given for R ₇ ,

R represents a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy or alkylsulfonyl group or an alkylthio or haloalkylthio group having 1 to 6 carbon atoms or a cycloalkyl or halocycloalkyl group or alkenyloxy, alkynylthio, alkynylthio, alkynylthio, alkynylthio, alkynylthio, alkynylthio or a nitro or cyano or amino group, optionally mono- or disubstituted by an alkyl or acyl group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenyl group, a phenoxy group or a pyridyloxy group, wherein: these groups are optionally substituted, their salts and optically active isomers, with the proviso that when n is 0 then the non-optically active moiety is derived from an optically active primary amine or from an optically active amine;

Some compounds belonging to the novel general formulas of the active amino acid.

to the 2-imidazolin-5-one group

are known for their herbicidal properties from European Patent Documents 41,623, 41,624, 215,738, 226,947, 261,705, 303,863, 433,655 and 436,483 and from US Patents 4,925,944, DE 3,913,757, GB 2,167,062, GB 2,192,877 and JP 3,196,570.

Imidazolinones of general formulas

X

have been described with respect to patent applications 1,176,660 and 1,258,412.

for their pharmaceutical properties in WO 9,114,679, JP 8,055,467 and DE

No fungicidal activity has been reported for the compounds of formula (I).

Compounds of formula Ia

are new compounds.

A) Compounds of formula Ib (n = 0) ^N 1 / ^R 3

II

W

(Ib) can be prepared by known methods described in the literature below.

1 °) Cyclization of the alpha-amino acid amide of formula II ^r 2 0 I ii

R] _-- C-NH-R ₄ ^(11>

nh _{2 a} carboxylic acid orthoester of the general formula

R-C (OR ') wherein R' represents a linear or branched alkyl group having 1 to 4 carbon atoms.

This method has been described, for example, by J. Brunken and G. Bach in Chem.Ber., 89, p. 1363-1373 (1956) or S. Ginsburg in J. Org. Chem., 27, p. 4062-4064 (1962).

Amino acid amides of formula II can be prepared by conventional reaction of an amine of formula R NH with an additional 4 rom of amino acid of formula III ^R 2 O

II c -OR (III)

This reaction can be carried out under the conditions described by J. Brunken and G. Bach in Chem. Ber., 89, p. 1363-1373 (1956).

20) Reaction of an amine of formula R NH with an imino ester of formula IV

R.

ROCO C — N ^:

(IV)

This method is described in J. Chem. Soc., 1959, p. 1648 G. Shaw et al.

Iminoesters of formula IV can be obtained by reacting an amino acid ester of formula III with an imidate of formula

OR ', which is described in Ber.dt.Chem.Ges., 47, p. 2545 (1914).

(30) Compounds of formula (Ib) in which H is hydrogen may be obtained by cyclization of isonitrile derived from amides of formula (V) in the presence of a base.

This method has been described in Belgian patent application 862,194 (filed December 22, 1977).

(40) Compounds of formula (Ib) may be obtained by alkylating compounds of formula (Ib ') in which R is hydrogen using a compound of formula (R 1) X in a basic environment as described in the above-mentioned Belgian patent application:

5 °) Reaction of an amine of formula R NH with azalactone 2 2 of formula VI

y * ³

O (VI)

This reaction may be carried out by an acid catalysis mechanism (for example using acetic acid) or basic catalysis. An example of the latter catalysis can be found in Ito.a et al., Yakugaku Zasshi, 1975, 95 (1), 28-32.

B) Compounds of formula Ia can be obtained in a manner analogous to the above process by reacting hydrazine derivatives of formula R 1 NR _{2 with} NH ₂ instead of amine derivatives of formula R 1 NH.

These compounds can also be prepared by a process forming part of the invention, i. j. cyclization at an elevated hydrazide temperature of formula VII:

R ₇ —C —ΝΉ — C — C-NH — N- ^R 4 ³ II | II

O r ₂ o

This reaction is catalyzed by acids. Inorganic acids, alkylsulfonic acids, arylsulfonic acids, acidic resins or carboxylic acids can be used in the function of these acids.

This reaction can be carried out in aromatic solvents, halogenated hydrocarbons, ethers, cyclic ethers, esters or alcohols.

The reaction is carried out at a temperature of 50-150 ° C. The reaction is usually carried out at the reflux temperature of the solvent, whereby the water formed is distilled off.

The hydrazides of formula (VII) may be prepared by any of the methods described in the literature, for example by the following methods.

1) Reaction of some hydrazines of the formula R ₄ NR ₅ NH ₂ with some methyl, ethyl, propyl or butyl esters of amino acids of the formula

R

R - C - NH - C - C - OR

II I II

R 0, which is described in German patent application 1,089,390 (filed Sep. 22, 1960 (Chem.Ab., 1962,56, pp.4860-4862)).

2) Condensation of N-acylated amino acids with hydrazine in the presence of papain extracts in a buffered aqueous solution described by Niemann and Nichols in J. Biol. Chem. , 146, 1942, pp. 191-201.

3) Reaction of a hydrazine of the formula R 1 NR _with NH 4 with an azalactone of the formula VI described in JP Branquet et al. in Bull. Soc. Chim. de France, 1965, (10), p. 2942-2954.

The azalactones of formula VI are also described in the aforementioned article.

(4) A preferred general method, analogous to (2), is to activate the acid in the imidazolide form (reaction a) or in the form of a mixed anhydride to condense it with hydrazine:

a)

R - C · O

--►

E-C-C-OH

N-t-CO

b) r ₂ σ

II o

r ₃ —c

-VII

R

R ₃ - C NH - C - C OH - C 1 CO ₂ R 4 - ΤΞΑ

I ¹ _

R ₃ —C-NH — c — C-O-C-OR- —vil π Γ || y - o ^R 2 o 0 R ₄ NR ₅ NH ₂

This condensation is carried out under the conditions customary for this type of reaction, as illustrated in Examples 1 and 2 below.

and

C) Another preferred process for the preparation of the compounds of formula Ia is to react the hydrazine R 1 NR 4 NH 4 with an azalactone of formula VI under the following conditions.

By heating the reactants in an inert solvent in the presence of an acid to catalyze the reaction. As the solvent, halogenated hydrocarbons, esters, aromatic solvents or alcohols can be used. Inorganic acids, alkylsulfonic acids, arylsulfonic acids, acidic resins or carboxylic acids can be used as catalysts for the reaction. The reaction is carried out at a temperature of 50 to 150 ° C.

This process is illustrated in Example 4 below.

) Heating the mixture of reactants in acetic acid under reflux in the presence of sodium acetate to catalyze the reaction.

This method is illustrated in Example 5.

D) Compounds of formula Ia in which R is other than hydrogen may also be prepared from compounds of formula Ia 'which can be alkylated, acylated, alkoxycarbonyllated, carbamoylated or sulfamoylated _with R5 in the presence of a base and a solvent of

(Ia ^{1) H} (Ia) ^R 5 wherein in the general formula R ₌ an alkyl, alkoxycarbonyl, acyl, aryl carbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl which is defined above, and X is a halogen atom, sulfate group, or an optionally a substituted phenoxy group or an alkylsulfonyloxy group or an arylsulfonyloxy group or an R _s O group when R _s is an acyl group.

As bases, alkali metal hydrides and alkoxides or a tertiary amine can be used. The reaction may be carried out at a temperature of -30 to 50 ° C. Ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide or aromatic solvents can be used as solvents, the calculation of the above solvents being exemplary only.

The carbamoylation or thiocarbamoylation of the compounds of formula Ia 'can be carried out using a reaction with isocyanates or isothiocyanates according to the reaction scheme:

This reaction is carried out under the conditions described above, although bases in catalytic amounts may be used.

E) Compounds of formula Ia in which R @ ₃ is hydrogen may be obtained by reacting dimethylformamide dimethylacetate (DMFDMA) with an aminohydrazine of formula VIII according to the following reaction scheme

RNH-N (VIII) ^{+ (ch} 3 ⁵ 2 ^{NCK (0CH} 3 ¹

in. x -? '4

V * 5

This reaction is carried out at 10 to 100 ° C in DMFDMA, which is used in excess.

Aminohydrazine intermediates of formula VIII can be obtained in a novel manner by reaction of the hydrochloride chloride of the corresponding alpha-amino acid in the presence of a base according to the following reaction scheme:

lähde: ✓ ^ 4 + · I ¹ Ci * 1

CI K-jN j ⁺ K ₂ NN _s -► H ₂ N — j R c 'R ₅ ' 0 r ₂ 3 R ₂ (VIII).

The reaction is carried out at a temperature between -20 to 40 ° C in cyclic or non-cyclic ethers. Nitrous organic bases such as triethylamine or pyridine can optionally be used as bases. Acid chloride intermediates can be obtained as described by S. Levine in J. AM.Chem.Soc. 1953, vol. 76, p. 1392. These compounds can thus be obtained by reacting phosphorus pentachloride with an alpha-amino acid according to the following reaction scheme:

: ₂ n ·

OH

C ⁺ o

&Quot; No "

Oi i 'O

Compounds which are preferred compounds due to their better fungicidal activity and / or their easier synthesis are:

(1) compounds of formula Ia;

2) compounds of formula I, in particular of formula Ia, in which R represents a hydrogen atom,

3) compounds in which R 1 and R ₂ are other than hydrogen,

4) compounds in which R ₂ represents a C 1 -C 3 alkyl group, preferably a methyl group,

5) compounds wherein R is phenyl optionally substituted with R _? .

6) compounds in which a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is optionally substituted by one or more substituents selected from the group consisting of a halogen atom, a methoxy group and a methylthio group,

7) compounds wherein the phenyl ring is optionally substituted with R _? and

8) compounds of formula I wherein W is O.

In the following, the invention will be further elucidated by means of specific examples thereof, the examples being illustrative only and not in any way limiting the scope of the invention, which is clearly defined by the wording of the claims. These examples illustrate the compounds of the invention, processes for their preparation and their antifungal properties. The structures of all products prepared in the above examples were verified by at least one spectroscopic technique selected from the group consisting of proton nuclear magnetic resonance spectroscopy, ¹³ C-nuclear magnetic resonance spectroscopy, infrared spectroscopy or mass spectroscopy. In the tables below, methyl, ethyl, propyl, butyl and phenyl are abbreviated as Me, Et, Pr, Bu and Ph.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

This example illustrates the preparation of the hydrazide of formula VII by method B) 4a)

Preparation of 2-propionylamino-2-phenyl-2'-phenylpropionohydrazide (Compound 102)

To a solution of 5.6 g (0.0253 mol) of N-propionyl-2-methyl-2-phenylglycine in 150 ml of anhydrous dichloromethane stirred under an inert atmosphere is added 4.51 g (0.0278 mol) Ν, Ν ' -carbonylimidazole, then the mixture is allowed to react until gas evolution ceases. Then, 3.28 g (0304304 mol) of phenylhydrazine is added and the mixture is allowed to react for 12 hours. The reaction mixture is then concentrated under reduced pressure and the residue is chromatographed on a column of 400 g of SiO2, eluting with a 65:35 mixture of ethyl acetate and heptane. The product fraction was then concentrated under reduced pressure to give 4.80 g (0.0154 mol) of 2-propionylamino-2-phenyl-2'-phenylpropionohydrazide.

Melting point: 144 DEG C. Yield: 61%.

In the same way, compounds 101 to 109 and 112 of the following table are obtained, which are intermediates for the preparation of compounds 1 to 9 and 12.

R □ _

I

R-C-NH-C-C-NH-NH-R

4

I

CH

no. R 1 R 3 R 4 yield MP: 101 ph Me ph 53% 150 ° C 102 ph et ph 61% 144 ° C 103 ph CF 3 ph 50% 161 ° C 104 ph CC1 3 ph 49% 187 ° C 105 ph nPr ph 55% 102 ° C 106 ph Pr ph 45% 130 [deg.] C 107 ph Bu ph 77% 134 ° C 108 4-Cl-Ph Me ph 71% Mp 180 ° C 109 4-Cl-Ph Me 2-Me-Ph 64% 152 ° C 112 ph C1CH 2 ph 55% 146 ° C

Example 2

Preparation of the hydrazide of formula VII by method B) 4b): N-trifluoroacetyl-2- (4-methylphenyl) glycine phenylhydrazide.

1.38 g (5 mmol) of N-trifluoroacetyl-2- (4-methylphenyl) glycine, 25 ml of anhydrous toluene and then 0.75 ml (5.5 mmol) of anhydrous triethylamine are introduced into a 100 ml round-bottomed flask. The reaction mixture was cooled to -15 ° C, then 0.475 mL (5 mmol) of ethyl chloroformate was added dropwise. A white precipitate formed and stirring was continued for 30 minutes at -10 ° C.

0.5 g (4.5 mmol) of phenylhydrazine and 25 ml of anhydrous toluene are introduced into a vacuum flask and the mixture is cooled to -15 ° C. The contents of the first round flask are quickly filtered through a glass frit into a Erlenmeyer flask containing phenylhydrazine. The reaction mixture was allowed to warm to ambient temperature, washed with dilute sodium hydroxide solution and water, then dried over magnesium sulfate, filtered and evaporated. 1.4 g (78% yield) of a white solid are obtained, having a melting point of 162 DEG C. and the formula:

Example 3

This example illustrates the preparation of compounds of formula Ia by method Ba to cyclization of compounds of formula VII: preparation

2,4-Dimethyl-4-phenyl-1-phenylamino-2-imidazolin-5-one (Compound No. 1).

A stirred solution of 1.5 g (0.005 mol) of 2-acetylamino-2-phenyl-2'-phenylpropionohydrazine and 0.17 g (0.001 mol) of paratoluenesulfonic acid in 25 ml of toluene is maintained at reflux for 7 hours while forming the water is removed. The reaction mixture is then concentrated under reduced pressure and the residue is chromatographed on 200 g of SiO using a mixture of ethyl acetate and heptane (50% / 50%). A dense oil is isolated which crystallizes after trituration in diisopropyl ether. After filtration, 0.5 g (0.0018 mol) of 2,4-dimethyl-4-phenyl-1-phenylamino-2-imidazolin-5-one (Compound No. 1) (yield 36%) was isolated as a white melting powder. at 135 ° C.

In the same manner, compounds 1 to 9 _and 12 of the formula are prepared using the corresponding reactants

which are listed in the following table.

no. R R 3 R 4th yield MP: 1 ph Me ph 36% 135 ° C 2 ph et ph 86% honey 3 ph CF 3 ph 66% 104 ° C 4 ph CC1 3 ph 14% 68 ° C 5 ph nPr ph 84% honey 6 ph Pr ph 69% 122 ° C 7 ph Bu ph 11% 87 ° C 8 4-Cl-Ph Me ph 54% 140 [deg.] C 9 4-Cl-Ph Me 2-Me-Ph 65% 142 ° C 12 ph C1CH 2 ph 79% 76 ° C 14 ph et ph 53% 78 ° C 15 ph et 2-Me-Ph 68% 107 ° C 16 ph Me 2-Me-Ph 53% 180 ° C 18 ph MeOCH 2 ph 8% 95 ° C 19 ph MeOCH 2 3-Cl-Ph 20% 125 [deg.] C 26 4-Me-Ph Me ph 41% 142 ° C 29 ph MeOCH 2 2-Me-Ph 54% 122 ° C 33 4-Me-Ph CF 3 ph 35% Mp 166 ° C 45 ph MeOCH 2 2,3-di-Me-Ph 55% 91 ° C

Example 4

Preparation of the compound of formula Ia by method c) 1): preparation

2,4-Dimethyl-4-phenyl-1-phenylamino-2-imidazolin-5-one (Compound No. 1)

A solution containing 0.9 g (4 mmol) of 2,4-dimethyl-4-phenyl-223 oxazolin-5-one, 0.43 g (4 mmol) of phenylhydrazine and 0.1 g of paratoluenesulfonic acid in 30 ml of toluene is heated to the reflux temperature for one hour. The water formed is removed by azeotropic distillation and the mixture is concentrated under reduced pressure. The crude product is then purified by chromatography on silica gel. Compound 1 is thus obtained in a yield of 25%.

In the same way 2,4-dimethyl-4- (4-chlorophenyl) 1- (2,3-dimethylphenylamino) -2-imidazolin-5-one (compound 10 in 18) was obtained.

Melting point: 164 ° C.

Example 5

Preparation of the compound of formula Ia by method C12): preparation

2,4-Dimethyl-4- (4-chlorophenyl) -1- (chlorophenylamino) -2-imidazolin-5-one (Compound No. 11).

A solution containing 1.5 g (6.7 mmol) of 2,4-dimethyl-4- (4-chlorophenyl) -2-oxazolin-5-one, 0.93 g (6.7 mmol) of 2-chlorophenylhydrazine and 0.25 g of sodium acetate in 20 ml of acetic acid was heated to reflux for 2 hours. The reaction mixture is concentrated under reduced pressure and the residue is dissolved in 150 ml of methylene chloride. The methylene chloride solution was washed with aqueous sodium bicarbonate solution and then with pure water. The solution is then concentrated and the product is purified by chromatography on silica gel, eluting with a mixture of ethyl acetate and heptane (30% / 70%). Compound 11 is thus obtained in a yield of 43%.

The same procedure gave compound 13 in 33.5% yield.

The same procedure also yields compounds of the general formula

CH whose chemical structure, the yield obtained and the melting point are given in the following table.

no. R R 3 R A yield MP: 13 4-Br-Ph Me ph 34% 147 ° C 17 4-Cl-Ph ph 3-Cl-Ph 31% 120 [deg.] C 20 ph Me 3-Cl-Ph 43% 163 ° C 21 4-Cl-Ph et ph 27% 144 ° C 22 4-Br-Ph Me 2-Me-Ph 38% 144 ° C 23 4-Br-Ph Me 2-Cl-Ph 41% 145 ° C 24 4-Br-Ph et ph 20% Mp 110 ° C 25 4-Cl-Ph Me Pr 53% honey 30 4-F-Ph Me ph - 150 ’C 31 Ph Me ph - Mp 192 ° C 32 Ph 2 et ph - Mp 167 ° C 34 ph Me 4-iPr-Ph 20% Mp 162 ° C 35 ph Me 2,3-dimethyl Ph 16% 64 ° C 36 ph Me 2,3-diCl-Ph 33% 165 [deg.] C 37 ph Me 2,4-dimethyl Ph 43% Mp 100 ° C 38 ph Me 3,4-dimethyl Ph 30% 135 ° C 39 ph Me 4-Cl-Ph 56% 68 ° C 40 ph Me 2-Cl-Ph 50% 196 ° C 41 ph Me 4-MePh 34% 142 ° C 42 ph Me 2-MePh 45% 129 ° C 43 ph et 3-Cl-Ph 26% 82 ° C 44 ph et 2,3-diCl-Ph 41% 60 ° C 46 ph et 3,4-dimethyl Ph 32% 94 ° C

no. R R 3 R yield MP: 47 ph et 2,3-dimethyl Ph 27% 109 ° C 48 ph et 2,4-dimethyl Ph 50% 45 ° C 49 ph et 4-Cl-Ph 48% 73 ° C 50 ph et 4-iPr-Ph 16% 73 ° C 51 ph et 2-Cl-Ph 56% 84 ° C 52 ph et 3-Me-Ph 14% 85 ° C 53 4-Ph-Ph Me ph 54% 134 ° C 56 4-Ph-Ph et ph 58% honey 59 3-Cl-Ph et ph 49% 117 ° C

Similarly, spiro compounds 27 (yield 56%, mp: 203 ° C) and 28 (yield 56%, mp: 153 ° C) of the formulas were obtained:

Example 6

Preparation of compounds of formula Ia, wherein R ₃ is H, and the intermediates of formula VIII, method E.

a) To a solution of 2.25 g (0.0208 mol) of phenylhydrazine in 50 ml of diethyl ether, 4.58 g (0.0208 mol) of methylphenylglycine hydrochloride hydrochloride was added in one portion and the suspension thus obtained was stirred for 18 hours. The suspension is then filtered, the solid is filtered off with suction and redissolved in distilled water. The resulting solution was slowly made alkaline to pH 7-8 using a saturated sodium bicarbonate solution. The precipitate thus formed is filtered off and washed with distilled water and then recrystallized from isopropanol. After filtering off the crystals and drying them under reduced pressure at 50 ° C, 2 g (0.0078 mol) of (2R, 2S) -2-amino-2-phenyl-2'-phenylpropionohydrazide (compound 155), m.p. 154 ° C. Yield: 38%.

• à

In like manner, the fenylpropi'onohydräzidy formula VIII, R, the ₂ n

NH-N <· ^Λ 5 (VIII) wherein the chemical structure, yield and melting point are given in the table below.

no. R X R 2 R R 5 Yield% MP: 155 ph Me ph H 38% 154 [deg.] C 157 ph Me 2-Me-Ph H 32% 115 ° C 158 ph Me 2-Cl-Ph H 20% 164 ° C 160 ph Me 2-Cl-Ph H 68% 112 ° C 161 ph Me 4-Cl-Ph H 48% 177 ° C

no. R 1 R 2 R R 5 Yield% MP: 163 ph Me 2-F-Ph H 43% 112 ° C 164 ph Me 4-F-Ph H 40% 142 ° C 165 ph Me 3-Me-Ph H 45% Mp 110 ° C 166 ph Me 4-Me-Ph H 26% Mp 168 ° C 167 ph Me 3-F-Ph H 33% 161 ° C

In a similar manner, spiro compound 162 was obtained (R = = (CH ₂ ) ₂ , R ₃ = H, = Ph, 7% yield, mp: 171 ° C).

b) (4R, 4S) -4- (4-Fluorophenyl) -4-methyl-1-phenylamino-2-imidazolin-5-one (Compound 54)

A solution of 2.73 (0.01 mol) of (2R, 2S) -2-amino-2- (4-fluorophenyl) 2'-phenylproionohydrazide in 16 ml of N, N-dimethylformamide dimethyl acetal was stirred for 48 hours. The reaction mixture is then concentrated under reduced pressure. The residue is then chromatographed on silica gel, eluting with a 50:50 mixture of n-heptane and ethyl acetate. Fractions containing pure product no. 54 is thickened together. 1.5 g (0.0053 mol) of (4R, 4S) -4- (4-fluorophenyl) -4-methyl-1-phenylamino-2-imidazolin-5-one, melting at 140 ° C, is isolated. (determined on the Kofler block). Yield: 53%.

In the same way, compounds of the formula Ia in which R represents a hydrogen atom, i. j. compounds of formula

whose chemical structure, yield and melting point are given in the following table.

no. R X R 2 R 4 Yield% MP: 54 4-F-Ph Me ph 53% 140 ° C 55 ph Me ph 38% 129 ° C 57 ph Me 2-Me-Ph 72% 175 ° C 58 ph Me 3-Cl-Ph 46% 177 ° C 60 ph Me 2-Cl-Ph 79% 176 [deg.] C 61 ph Me 4-Cl-Ph 33% 153 ° C * 62 C H e 4, (CH) ph 64% 202 ° C 63 ph Me 2-F-Ph 86% 151 ° C 64 ph Me 4-F-Ph 40% 124 ° C 65 ph Me 3-Me-Ph 50% 109 ° C 66 ph Me 4-Me-Ph 41% 127 ° C 67 ph Me 3-F-Ph 20% 137 ° C

*) spiro compound

Example 7

In vivo test for Plasmopara viticola (vine peronospora)

An aqueous suspension of the active substance to be tested is obtained by fine grinding having the following composition:

Active ingredient: 60 mg Tween 80 surfactant (polyoxyethylene sorbitan oleate) diluted to 10% with water: 0.3 ml volume is adjusted to 60 ml with water.

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

Chardonnay grape chunks (Vitis vinifera) are grown in small pots. When these plants are two months old (eight to ten leaf stage, 10 to 15 cm high), they are sprayed with the above aqueous suspension.

The plants used for control are treated with an aqueous solution which does not contain the active substance.

After drying for 24 hours, each plant is infected by spraying with an aqueous spore suspension of Plasmopara viticola, a suspension obtained from a 4 to 5 day culture subsequently suspended at a concentration of 100,000 units per cm ³ .

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

Evaluation is carried out seven days after infection by comparison with control plants.

Under these conditions, good (at least 75%) or complete protection of the following compounds is observed at a dose of 1 g / l: 1, 2, 3, 13, 15 to 18, 20 to 22, 24, 26 to 30, 35, 37 to 57 , 59-62, 64-67.

Example 8

In vivo test for Puccinia recondita (wheat rust)

An aqueous suspension of the active substance to be tested is obtained by fine grinding having the following composition:

Active ingredient: 60 mg Tween 80 surfactant (polyoxyethylene sorbitan oleate) diluted to 10% with water: 0.3 ml volume is adjusted to 60 ml with water.

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

Wheat sown in small pots into the substrate of the 50:50 mixture of peat and hardened volcanic tuff is treated at the 10 cm stage by spraying with the above aqueous suspension.

After 24 hours, an aqueous spore suspension (100,000 spores / cm ³ ) is sprayed on wheat. This suspension is obtained from infected germ. The wheat is then placed in an incubation chamber at about 20 ^° C at 100% RH for 24 hours and then at 60% RH for 7-14 days.

Monitoring of germinal plant status is performed between day 8 and day 15 after infection by comparison with untreated control plants.

Under these conditions, good (at least 75%) or complete protection is observed at 1 g / l for the following compounds: 1, 2, 3, 8, 12, 17, 21, 22, 24, 28, 30, 35, 53, 54, 56, 59.

Example 9

In vivo test for Phytophtora infestans

By finely grinding, an aqueous suspension of the active substance to be tested, having the following composition, is prepared:

active ingredient: 60 mg Tween 80 surfactant (polyoxyethylene sorbitan oleate) diluted to 10% with water: 0.3 ml volume is adjusted to 60 ml with water.

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

Tomato seedlings (Marmande variety) are grown in pots. When these seedlings are one month old (stage 5 to leaves, plant height 12 to 15 cm), they are sprayed with an aqueous suspension having the above composition. Sprayed suspensions have different concentrations of the test drug.

After 24 hours, each plant is infected by spraying with an aqueous spore suspension of Phytophtohora infestans.

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

Seven days after infection, the results obtained for the plants treated with the test drug are compared with those obtained for the control plants. Under these conditions, at a dose of 1 g / l, good (at least 75%) or complete protection is obtained for the compounds: 1, 2, 13, 18, 21, 49, 54.

It is clear from the above results that the derivatives of the invention have good fungicidal properties and that the derivatives of the invention are able to provide plants with protection against fungal plant diseases caused by fungi belonging to various classes, such as

Phycomycetes

Basidiomycetes

Ascomycetes,

Adelomycetes or fungi imperfecti, in particular against peronospore of grapevine, wheat rust and mold fungus.

In practice, the compounds of the invention are rarely used alone. In most cases, these compounds form part of the compositions. These compositions, which can be used as fungicidal agents, contain as active ingredient the compound (s) of the invention described above, in admixture with a solid or liquid carrier which is acceptable for agricultural purposes and with surfactants which are also acceptable for agricultural purposes. In particular conventional inert carriers and conventional surfactants can be used in this regard.

These compositions also form part of the invention.

These compositions may also contain all kinds of other ingredients, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, complexing agents, and the like. More generally, the compounds used in the invention can be used in combination with any solid or liquid additives that correspond to conventional formulation techniques.

In general, the compositions of the invention usually contain about 0.05 to 95% (w / w) of a compound of the invention (hereinafter called the active ingredient), one or more solid or liquid carriers and optionally one or more surfactants.

The term "carrier" as used herein refers to a natural or synthetic, organic or inorganic material with which a compound is mixed to facilitate its application to plants, seeds, or soil. This carrier is therefore generally inert and must be acceptable in agriculture, especially for treated plants. The carrier may be solid (clays, natural or synthetic silicates, silicas, resins, waxes, solid fertilizers, and the like) or liquid (water, alcohols, especially butanol, and the like).

The surfactant may be an emulsifier, dispersant or wetting agent of the ionic or non-ionic type, or a mixture of such surface-active acids, lignosulfonic acid salts, phenolsulfonic or naphthalenedulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols, fatty acids or fatty phenols ), salts of sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylenated alcohols or phenols, fatty acid esters and polyols, and derivatives of the above compounds containing sulfate, sulfonate or phosphate functional groups. The presence of at least one surfactant is generally indispensable when the compound and / or the inert carrier is insoluble in water and water is used as the carrier for application.

The compositions for agricultural use according to the invention may thus contain the active compounds according to the invention in a very wide range, from 0.05% to 95% by weight. The surfactant content of the compositions preferably lies between 5% by weight. and 40 wt%.

The compositions of the invention may be in very diverse, solid or liquid forms.

Solid form preparations include dusts (containing up to 100% compound) and granules, particularly granules obtained by extrusion, compression, impregnation of a granular carrier, or granulation from a powder (the compound content of these granules lies between 0.5 to 80% for the latter examples), tablets and effervescent tablets.

The compounds of formula (I) may also be used in the form of dusts, a composition containing 50 g of active ingredient and 950 g of talc may be used, a composition containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc may also be used. These ingredients are mixed and ground and applied as a dusting agent.

Formulations which are liquid or intended to form liquid compositions at the time of application include solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wetting powders (or powders for application by spray), pastes or gels .

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

In addition to the solvent, the emulsifiable concentrates may contain, if necessary, 2 to 20% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives listed above.

By diluting these concentrates with water, emulsions of any desired concentration can be obtained, which are particularly suitable for application to crops.

As an example, the composition of several emulsifiable concentrates is now given:

Example EC 1 active substance 400 g / l alkali metal dodecylbenzenesulfonate 24 g / l

- oxyethylenated nonylphenol containing 1 mol of ethylene oxide 16 g / l cyclohexanone 200 g / l aromatic solvent to be added to 1 l

According to another regulation for emulsifiable concentrate:

Example EC 2 active substance epoxidized vegetable oil

250 g g

mixture of alkylarylsulfonate and polyglycol ether and fatty alcohols dimethylformamide xylene

100 g g

575 g

Suspension concentrates, which can also be applied by spraying, are prepared so as to form a stable, non-settling liquid product, and generally contain from 10 to 75% active ingredient, from 0.5 to 15% surfactants, from 0.1 up to 10% of thixotropic agents, and from 0 to 10% of suitable additives such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrating agents and adhesives, and as a carrier, water or organic liquid in which the active substance has poor solubility, or it is insoluble: some solid organic substances or inorganic salts may be dissolved in the carrier to prevent sedimentation or as antifreeze for water.

As an example, the suspension concentrate is now combined:

Example SC 1 active ingredient 500 g polyethoxylated tristyrylphenyl phosphate 50 g

- polyethoxylated alkylphenol 50 g sodium polycarboxylate 20 g ethylene glycol 50 g organopolysiloxane oil (antifoam) 1 g polysaccharide

1.5 g water 316.5 g

Soaking powders (or powders for spray application) are generally prepared containing 20 to 95% active ingredient, and generally contain, in addition to a solid carrier, 0 to 30% wetting agent, 3 to 20% dispersing agent and, if necessary, 0.1 to 10% of one or more stabilizers and / or other additives such as penetration agents, adhesives, anti-caking agents, colorants and the like.

In order to obtain sprayable or wetting powders, the active ingredients are intimately mixed in suitable mixers with other ingredients and the mixture is ground in mills or other suitable crushers. Powders for spray application are thus obtained which exhibit advantageous wettability and suspensibility. They can be suspended in water at any desired concentration, and these suspensions can be used very advantageously in particular for application to plant leaves.

Pastes can be made instead of soaking powders. The conditions and methods for the production and use of these pastes are similar to those of dipping or spraying powders.

As an example, the composition of the various soaking powders (or powders for spray application) is now given:

Example WP 1 Active ingredient 50% ethoxylated fatty alcohol (wetting agent) 2.5% ethoxylated phenylethylphenol (dispersant) 5% chalk (inert carrier) 42.5%

Example WP 2 active substance%

C synthetic branched chain oxoalcohol ethoxylated 8 to 10 moles ethylene oxide (wetting agent) 0,75% neutral calcium-lignosulfonate (dispersant) 12% calcium carbonate (inert filler) supplement up to 100%

Example WP 3

This soaking powder contains the same ingredients as in the above example, in the ratios below:

Active ingredient 75% Wetting agent 1.50% Dispersing agent 8% Calcium carbonate (inert filler) Supplement up to 100%

Example WP 4 Active ingredient 90% ethoxylated fatty alcohol (wetting agent) 4% ethoxylated phenylethylphenol (dispersant) 6%

Example WP 5 Active ingredient 50% anionic and nonionic surfactant mixture (wetting agent) 2.5% sodium lignosulfonate (dispersant) 5% kaolin (inert carrier) 42.5%

Included within the overall scope of the invention are aqueous dispersions and emulsions, for example compositions obtained by not diluting the soaking powder or emulsifiable concentrate of the invention with water. The emulsions may be of the water-in-oil or oil-in-water type and may have a thick consistency, such as mayonnaise ”.

The compounds of the invention may be incorporated into the form of water dispersible granules, which are also included within the scope of the invention.

These dispersible granules, with an apparent density lying generally between about 0.3 and 0.6, have a particle size generally between about 150 and 2000 µm and preferably between 300 and 1500 µm.

Active ingredient content between about 1% and 90%, and 90%.

in these granules lie generally and are preferably between about 25%

The remainder of the granule consists essentially of a solid filler and, optionally, a surfactant adjuvant, which ensures the dispersibility of the granule in water. These granules may have essentially two different types depending on whether the filler is water soluble or insoluble. If the filler is water-soluble, it may be inorganic or, preferably, organic. Excellent results were obtained with urea. In the case of an insoluble filler, the filler is preferably inorganic, such as kaolin or bentonite. The filler is preferably in combination with surfactants (in an amount of 2 to 20 wt.% Granules) of which more than half is formed, for example, by at least one substantially anionic dispersant such as an alkali metal or alkaline earth metal polynaphthalenesulfonate or lignosulfonate an alkali metal or an alkaline earth metal, and the remainder being nonionic or anionic to a wetting agent such as an alkali metal or alkaline earth metal alkyl naphthalenesulfonate.

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

The granules of the invention can be prepared by mixing the necessary ingredients and then granulating according to several methods known in the art (granulator, fluid bed, spraying, extrusion, and the like). Generally, the preparation is completed by crushing and then sieving through sieves to the desired particle size within the aforementioned range.

Preferably, these granules are obtained by extrusion, the preparation being carried out as described in the examples below.

Example DG 1

Dispersible granules% by weight. of the active substance and 10% urea in the form of beads are mixed in a mixer. The mixture is then ground in a pin mill. A powder is obtained which is moistened with approximately 8% by weight. water. The wet powder is extruded in a perforated cylinder extruder. Granules are obtained which are dried and then crushed and screened to obtain only granules of between 150 and 2000 µm.

Example DG 2

Dispersible granules

The following ingredients are mixed in the mixer:

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

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

Said granules may be used alone or in solution or dispersion in water to achieve the desired dosage. They can also be used to form combinations with other active substances, in particular fungicides, in the form of wetting powders or granules or aqueous suspensions.

With regard to compositions which are suitable for storage and transport, it is preferred that they contain from 0.5 to 95% by weight of active ingredient.

Another object of the invention is the use of the compounds according to the invention for combating fungal diseases by means of preventive or curative treatment of the plants or the place where the plants grow.

The compounds according to the invention are preferably applied at doses of 0.005 to 5 kg / ha and in particular at doses of 0.01 to 1 kg / ha.

Claims (27)

Compounds containing an imidazolinone or imidazolinethione group of the general formula I in which W is sulfur or oxygen, n is 0 or 1, A is NR _a, or O or S or ₆ or an CR__R S0__ or C = 0, R and R, 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 having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl or alkenylaminoalkyl; (C 2 -C 6) or (C 3 -C 7) dialkylaminoalkyl or cycloalkyl or (C 7 -C 5) aryl or aryl group comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, quinolyl or a methylenedioxyphenyl group and optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group, the aryl and alkyl radicals having the meanings given above, or R 2 and R ₂ together with the oxygen atom to which they are attached to the ring may form a carbocyclic or heterocyclic group containing 5 to 7 atoms, which rings may be condensed to an optionally substituted phenyl ring 1 to 3 groups selected from the meanings given for R _? . R represents a hydrogen atom or an alkyl or haloalkyl group having from 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group containing from 1 to 6 carbon atoms; (2-6 carbon atoms) or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3-6 carbon atoms; or Ν, Ν-dialkylcarbamoylalkyl having 4 to 8 carbon atoms, R represents a hydrogen atom when n is equal to 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 dialkylaminoalkyl, an alkylcarbamoylalkyl group having 3 to 6 carbon atoms; or 4, Ν-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyridazines a benzothenyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl group and optionally substituted with 1 to 3 groups selected from R _a or arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl, said aryl group being the aforesaid, or an amino group which is disubstituted by 2 same or different groups selected from the group consisting of: - (C1-C6) -alkyl, - an alkoxyalkyl, alkenyl or alkynyl group containing from 3 to 6 carbon atoms, - a cycloalkyl group containing 3 to 7 carbon atoms, - arylalkyl, phenyl or naphthyl, as defined above, optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? or - thienylmethyl or furfuryl, pyrrolidino, piperidino, morpholino or piperazino, optionally substituted with alkyl having 1 to 3 carbon atoms, represents a hydrogen atom when R _{4 is} not hydrogen, or alkyl, haloalkyl, alkylsulphonyl or alkylsulphonyl; (C 1 -C 6) -alkyl or (C 2 -C 6) -alkoxycarbonyl, (C 1 -C 6) alkoxyalkyl, (C 1 -C 6) alkoxyalkyl, (C 2 -C 6) alkoxycarbonyl or a formyl group or a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl group having 3 to 6 carbon atoms or cycloalkylcarbonyl C 4 -C 8 or phenyl, arylalkylcarbonyl, in particular phenylacetyl and phenylpropionyl, arylcarbonyl, especially benzoyl, optionally substituted with 1 to 3 groups selected from R, thienylcarbonyl, furylcarbonyl, benzyloxycarbonyl, furfuryloxycarbonyl, tetrahydrofurfuryloxykarbonylovú group, tienylmetoxykarbonylovú group, pyridylmetoxykarboriylovú, phenoxycarbonyl or (phenylthio) carbonyl, wherein the phenyl group itself being optionally substituted by from 1 to 3 groups selected from the meanings of _R? , (alkylthio) carbonyl, (haloalkylthio) 45 carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl, (furfurylthio) carbonyl, (tetrahydrofurfurythio) carbonyl, (thienyl) carbonyl, (thienyl) carbonyl, (thienyl) carbonyl), , (pyridylmethylthio) carbonyl or arylsulphonyl or carbamoyl, optionally mono- or disubstituted by alkyl or haloalkyl of 1 to 6 carbon atoms or cycloalkyl, alkenyl or alkynyl of 3 to 6 carbon atoms, alkoxyalkyl, alkylthioalkylthio having 2 to 6 carbon atoms or a phenyl group, optionally substituted with 1 to 3 groups selected from the meanings indicated for R1, a sulfamoyl group, optionally mono- or disubstituted - an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms or a phenyl group optionally substituted by 1 to 3 groups selected from the meanings given for R _? , (C 3 -C 8) alkylthioalkylsulfonyl or (C 3 -C 7) cycloalkylsulfonyl group, R is 6 hydrogen or cyano or C 1 -C 6 alkyl or C 3 -C 7 cycloalkyl or C 2 -C 6 acyl or alkoxycarbonyl or benzoyl optionally substituted with 1 to 3 groups selected from meanings given for R _? . R represents a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy or alkylsulphonyl group or an alkylthio or haloalkylthio group containing from 1 to 6 carbon atoms or a cycloalkyl or halocycloalkyl group or alkenyloxy, alkynylthio, or alkynylthio, or alkynyl, or alkynyl, carbon atoms or a nitro or cyano or amino group, optionally mono- or disubstituted by an alkyl or acyl group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenyl group, a phenoxy group or a pyridyloxy group wherein these groups are optionally substituted, their salts and optically active isomers, with the proviso that: - when n = 0, then the non-optically active residue is derived from an optically active primary amine or an optically active amino acid, - when n = 1, then A-R 6 is other than an optically active residue derived from an optically active primary amine or an optically active amino acid, - when n is 1 and A is S0 _2, then one of the two groups, or R ₂ is necessarily an aryl group, when R and R R are both phenyl, then n is 1, and - where R and R ₂ simultaneously represent a p-methoxyphenyl group, n is equal to the first 2. The compound of claim 1 of formula Ia wherein R and _R and W are as defined in claim 1. 3. The compound of claim 1 or 2, wherein R _p is hydrogen. 4. A compound according to any one of Claims l to 3, wherein R _x and R are other than hydrogen. Compounds according to any one of claims 1 to 4, wherein R ₌ represents an alkyl group containing 1 to 3 carbon atoms. Compounds according to claim 5, in which R 1 represents a methyl group. Compounds according to any one of claims 1 to 6, wherein R represents a phenyl group, optionally substituted by an R 6 group _. Compounds according to any one of claims 1 to 7, wherein R 1 represents an alkyl group having 1 to 3 carbon atoms and optionally substituted by one or more substituents selected from the group consisting of halogen atoms, methoxy and methylthio. Compounds according to any one of claims 1 to 7, wherein R ₃ represents a hydrogen atom. Compounds according to any one of claims 1 to 9, in which is a phenyl group optionally substituted by an R group. Compounds according to any one of claims 1 to 10, wherein W represents an oxygen atom. A fungicidal composition, characterized in that it contains, in combination with one or more solid or liquid agriculturally acceptable carriers and / or agriculturally acceptable surfactants, one or more active compounds consisting of compounds of the general formula ktorom in which: W is S or O or S = O, n is 0 or 1, A is NR _a, or O or S or CR _a R _e, or SO ^, or C = O, R and R, 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 an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl or alkenylalkyl group; (C 2 -C 6) or (C 3 -C 7) dialkylaminoalkyl or cycloalkyl or (C 1 -C 7) aryl or aryl group comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or isoquinolyl and optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group, wherein the aryl and alkyl radicals have the meanings given above, or R and _R may together with the oxygen atoms to which they are attached to the ring, form a carbocyclic or heterocyclic radical having 5 to 7 atoms, which rings may be fused to a phenyl ring optionally substituted with 1 to 3 groups selected from the meanings of . R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms or a (N) -alkyloxycarbamoyl or alkoxyalkyl group; Or 6 carbon atoms N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms, R represents a hydrogen atom when n is equal to 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 dialkylaminoalkyl, dialkylaminoalkyl, (C 3 -C 6) alkylcarbamoylalkyl; N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an aryl group comprising phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyridiminyl, pyrimidinyl a benzothenyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl group and optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl group, wherein the aryl and alkyl radicals have the meanings given above, or an amino group which is disubstituted by 2 of the same or different groups selected from the group consisting of - (C1-C6) -alkyl, - an alkoxyalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, - a cycloalkyl group containing 3 to 7 carbon atoms, an arylalkyl, phenyl or naphthyl group as defined above optionally substituted with 1 to 3 groups selected from the meanings given for R _? or - thienylmethyl or furfuryl, pyrrolidino, piperidino, morpholino or piperazino, optionally substituted with 1 to 3 carbon atoms, R is S is hydrogen when it is not hydrogen, or alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl of 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, alkylsulfonyl, alkoxycarbonyl, alkoxy, haloalkoxy, alkoxyalkyl 6 carbon atoms or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl group containing from 3 to 6 carbon atoms or a formyl group or a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl group containing from 8 to 6 carbon atoms , aryalkylcarbonyl, especially phenylacetyl and phenylpropionyl, arylcarbonyl, especially benzoyl, optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? thienylcarbonyl, furylcarbonyl, pyridylcarbonyl, benzyloxycarbonyl, furfuryloxycarbonyl, tetrahydrofurfuryloxycarbonyl, thienylmethoxycarbonyl, pyridylmethoxycarbonyl, optionally substituted phenoxycarbonyl, phenoxycarbonyl, phenoxycarbonyl or phenoxycarbonyl for R ₇ , (alkylthio) carbonyl, (haloalkylthio) carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl, (furfurylthio) carbonyl, (tetrahydrofurfurythio) carbonyl phenyl) carbonyl group a (pyridylmethylthio) carbonyl group or an arylsulfonyl group or a carbamoyl group, optionally mono- or disubstituted an alkyl or haloalkyl group containing 1 to 6 carbon atoms, or - a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, - an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? , a sulfamoyl group, optionally mono- or disubstituted an alkyl or haloalkyl group containing 1 to 6 carbon atoms, or - a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, - an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R _? , (C 3 -C 8) alkylthioalkylsulfonyl or (C 3 -C 7) cycloalkylsulfonyl group, R is G is hydrogen or cyano or (C1-C6) alkyl or (C3-C7) cycloalkyl or (C2-C6) acyl or alkoxycarbonyl or benzoyl optionally substituted by 1 to 3 groups selected from the meanings indicated for R ^, R represents a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy or alkylsulfonyl group or an alkylthio or haloalkylthio group having 1 to 6 carbon atoms or a cycloalkyl or halocycloalkyl group or alkenyloxy, alkynylthio, alkynylthio, alkynylthio, alkynylthio, alkynylthio, alkynylthio or a nitro or cyano or amino group, optionally mono- or disubstituted by an alkyl or acyl group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenyl group, a phenoxy group or a pyridyloxy group, wherein: these groups are optionally substituted, their salts and optically active isomers. and A fungicidal composition according to claim 12, characterized in that it comprises from 0.05 to 95% by weight of the compounds according to the invention. A, any of claims 1 to 11. A method of treating crop plants which are infected with or susceptible to fungal diseases, characterized in that an effective amount of a compound according to any one of claims 1 to 11 or a composition according to claim 12 or 13 is applied preventively or curatively. A method according to claim 14, characterized in that X is an effective amount of 0.005 to 5 kg / ha. The method according to claim 15, characterized in that the effective amount is 0.01 to 1 kg / ha. A process for the preparation of compounds of formula Ia, characterized in that the compound of formula VII (VII) is cyclized in a hot solvent by catalysis with acid. Process according to claim 17, characterized in that the acid is selected from the group consisting of inorganic acids, alkylsulfonic acids, arylsulfonic acids, acidic resins and carboxylic acids. 19. The process of claim 17 wherein the solvent is selected from the group consisting of aromatic X solvents, halogenated hydrocarbons, ethers, cyclic ^ethers,? esters or alcohols. Process according to Claim 17, characterized in that it is carried out at a temperature of 50 to 150 ° C. 21. A process for the preparation of compounds of the formula Ia (Ia) by reacting a hydrazine of the formula R NR NH with a azalactone of the formula Λ S 2 ^{L of} formula VI -Λ Λ in an inert solvent in the presence of an acid to catalyze the reaction. 22. The process of claim 21 wherein the solvent is selected from the group consisting of aromatic solvents, halogenated hydrocarbons, esters, and alcohols. 23. The method of claim 21 wherein the acid is selected from the group consisting of inorganic acids, alkylsulfonic acids, arylsulfonic acids, acidic resins, or carboxylic acids. A process according to claim 21, characterized in that it is carried out at a temperature of 50 to 150 ° C. A process according to claim 21, characterized in that the hydrazine of the formula R NR NH and the azalactone of the formula VI are heated to reflux in acetic acid in the presence of sodium acetate to catalyze the reaction. 26. A process for the preparation of compounds of formula Ia, wherein R ₃ is H, characterized in that the dimethylphenyl ormamiddimetylacetal treated with aminohydrazínom of formula VIII according to equation ₂ NNR _{(c-3) 2} CH _{(OCH3) 2} (VIII) (la) Process according to claim 26, characterized in that the reaction is carried out at a temperature of 10 to 100 ° C, preferably in an excess of dimethylformamide dimethyl acetal.