CZ333894A3 - 2-imidazolin-5-one and 2-imidazoline-5-thione derivatives, process of their preparation and fungicidal composition containing said 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

From sr> o lq o

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The invention relates to novel imidazolinone or imidazolinthione compounds which are useful for plant protection. The invention also relates to processes for preparing said compounds and products, which may optionally be used as intermediates in said processes for preparing 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 combating fungal diseases of crops using said compounds.

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

It is a further object of the invention to provide compounds which also have an improved application spectrum for combating fungal diseases of crops.

It has now been found that these objectives can be achieved by 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

7 (/

in which

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

A is NR @ 4 or an oxygen or sulfur atom, or CR @ 6 R @ 8 or SO @ 8 or C = O,

R ₁ and R 8, which are the same or different, represent a hydrogen atom, provided that one of the two groups is different from the hydrogen atom, or an alkyl or haloalkyl group containing 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl C 2 -C 6 or C 3 -C 7 dialkylaminoalkyl or cycloalkyl or aryl comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl 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 are as defined above, or

R 6 and R 8 together with the carbon atom to which they are attached on the ring may form a carbocyclic or heterocyclic ring

- a 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 7, represents a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl , alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl having 2 to 6 carbon atoms, or

R is a dialkylaminoalkyl, alkoxycarbonylalkyl or Nalkylcarbamoylalkyl group having 3 to 6 carbon atoms, or

N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms means a hydrogen atom when n is 1 or alkyl having 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl containing (2-6 carbon atoms) or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3-6 carbon atoms; or

N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl and optionally substituted with 1 to 3 groups selected from R z or arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl, wherein the aryl and alkyl radicals are as defined above, or an amino group which is disubstituted by 2 same or different groups selected from the group consisting of

- an alkyl group containing 1 to 6 carbon atoms,

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

- cycloalkyl having 3 to 7 carbon atoms,

- an arylalkyl, phenyl or naphthyl group as defined above, optionally substituted with up to 3 groups selected from the meanings indicated for R 6, or

- thienylmethyl or furfuryl, pyrrolidino, piperidino, morpholino or piperazino, optionally substituted with 1 to 3 carbon atoms,

R _g represents a hydrogen atom when R 6 is not a hydrogen atom or an alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl or alkoxyalkyl a group containing 2 to 6 carbon-

and 6 carbon atoms or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl group having 3 to 6 carbon atoms or a formyl group or a cycioalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl group having 3 to 6 carbon atoms or a cycloalkyl group arylalkylcarbonyl, especially phenylacetyl and phenylpropionyl, arylcarbonyl, especially benzoyl, optionally substituted with 1 to 3 groups selected from R z, thienylcarbonyl, furylcarbonyl, pyridylcarbonyl, benzyloxycarbonylcarbonyl, furfurfuryloxycarbonyl, furfuryl , thienylmethoxycarbonyl, pyridylmethoxycarbonyl, phenoxycarbonyl or (phenylthio) carbonyl; wherein the phenyl group itself is optionally substituted with 1 to 3 groups selected from the meanings given for R 6, (alkylthio) carbonyl, (haloalkylthio) carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl a (furfurylthio) carbonyl group, a (tetrahydrofurfurylthio) carbonyl group, a (thienylmethylthio) 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 cycioalkyl, alkenyl or alkynyl group

W 1 containing 3 to 6 carbon atoms,

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

- a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R 6, 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, or

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

- a phenyl group optionally substituted by 1 to 3 groups selected from the meanings indicated for R1, an alkylthioalkylsulfonyl group containing 3 to 8 carbon atoms or a cycloalkylsulfonyl group containing 3 to 7 carbon atoms,

R 8 represents a hydrogen atom or a cyano or C 1 -C 6 alkyl group or a C 3 -C 7 cycloalkyl group or a C 2 -C 6 acyl or alkoxycarbonyl group or a benzoyl group optionally substituted by 1 to 3 groups selected from the meanings given 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 halo-cycloalkyl group, or

(C 3 -C 6) alkenyloxy, alkynyloxy, alkenylthio or alknylthio or nitro or cyano or amino, optionally mono- or disubstituted (C 1 -C 6) alkyl or acyl or alkoxycarbonyl 2-6 carbon atoms, phenyl, phenoxy or pyridyloxy, optionally substituted, salts and optically active isomers thereof, with the proviso that when n is 0, R 1 is other than optically an active moiety derived from an opically active primary amine or an optically active amino acid.

Some compounds belonging to the group of 2-imidazolin-5ones of the general formulas

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

seSiSS

have been described with respect to their pharmaceutical properties in patent applications WO 9,114,679, JP 8,055,467 and DE 1,176,660 and 1,258,412.

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

Compounds of formula (Ia)

are new compounds.

A) Compounds of formula 1b (n = 0)

may be prepared by known methods described in the literature, which are set forth below.

1 °) Cyclization of an alpha-amino acid amide of formula II ^r 2 O

(II)

NH is a carboxylic acid orthoester of the formula r ₃ -c (or ') ₃ wherein R' is a linear or branched alkyl group having 1 to 4 carbon atoms.

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

Amino acid amides of formula II may be prepared

1 by conventional reaction of an amine of formula R 1 N 1 with an amino acid ester of formula III

R,

OR (III)

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

2 °) Reaction of an amine of the formula R 4 N 1 with an imino ester of the formula IV

ROCO-C — N = (IV)

STEED'

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

The iminoesters of formula (IV) can be obtained by reaction of an amino acid of formula (III) with formula (II) by reaction with an imidate of formula

NH

STEED'

described in Ber.dt.Chem.Ges., 47, p.2545 (1914)

3 °) Compounds of formula (1b) in which it 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).

/

4 °) Compounds of formula 1b may be obtained by alkylation of compounds of formula 1b 'wherein R ₂ is hydrogen using a compound of formula R ₂ X in a basic environment as described in the aforementioned Belgian patent application:

of formula 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 et al., Yakugaku Zasshi, 1975, 95 (1), 28-32.

B) Compounds of formula (Ia) may be obtained in a manner analogous to the above process by reacting in the reaction of hydrazine derivatives of formula R4NR5NH2 instead of amine derivatives of formula R ^NHj.

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

C NH — N R 4 (VII)

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 to 150 ° C. Typically, the reaction is carried out at the reflux temperature of the solvent, whereby the water formed is distilled off.

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

) Reaction of some hydrazines of the formula R 3 NR 3 -N-4 with certain methyl, ethyl, propyl or butyl esters of amino acids of the formula R ₃

OR 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., 143, 1942, pp. 191-201.

ββ

3) Reaction of a hydrazine of the formula R 1 NR 8 NH 3 with an azalactone of the formula VI described in J.P.Branquet et al. in Bull. Soc.Chim. de France, 1965, (10), pp. 2942-2954.

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

4) A preferred general method analogous to paragraph

2) consists in the activation of the acid in the imidazolide form (reaction a) or in the form of mixed anhydride in order to condense it with hydrazine:

and)

Rt — C '

II o

-NH-C-C-OH

II o

(b)

r = C-nh

II o

t '.

N.

NCO

- * YLL r ₄ n ₅ nh ₂ t C1CO ₂ R + · TEA

-STEED

- BODY ^R 2 OO 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.

C) Another preferred process for the preparation of the compounds of formula (Ia) is by reacting the hydrazine R @ 1 NR @ 4 N @ 1 - with an azalactone of formula VI under the following conditions.

1 °) Heating the reactants in an inert solvent in the presence of an acid to catalyze the reaction. Halogenated hydrocarbons, esters, aromatic solvents or alcohols may be used as solvents. 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 method is illustrated in Example 4 below.

2 °) 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 wherein R 8 is other than hydrogen may also be prepared from compounds of formula Ia ', which may be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulfamoylated with R 5X in the presence of a base and a solvent

wherein, in the general formula, is alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl as defined above and X is halogen, sulfate or optionally substituted phenoxy or alkylsulfonyloxy or arylsulfonyloxy or -R RO in the case where R ^ represents an acyl group.

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

Carbamoylation or thiocarbamoylation of the compounds of formula (Ia ') may be carried out by reaction with isocyanates or isothiocyanates according to the reaction scheme:

This reaction is carried out under the conditions described above, although it is possible to use the base in catalytic amounts.

E) Compounds of formula (Ia) in which the symbol represents a hydrogen atom may be obtained by reacting dimethylformamide dimethyl acetate (DMFDMA) with an aminohydrazide of formula (VIII) according to the following reaction scheme • 1 e ₂ n (VIII)

* X '

-v ^r 5

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

Aminohydrazide 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:

or h ₃ n'1 Cl 2

Λ ⁺ K ₂ NN _s * · k _{2 n} 1 NH Ν _χ ^T —-R

O (VIII).

The reaction is carried out at a temperature between -20 and 40 ° C in cyclic or non-cyclic ethers. Nitrous organic bases such as triethylamine or pyridine may optionally be used as bases. The acid chloride intermediates can be obtained as described by S. Levine in J. Am. Chem. 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:

^R 1 OH - + - 1 1 Cl ⁺ PC1 ₅ -► Cl e ₃ jt-7-ζ η O 'o

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

(1) compounds of formula (Ia);

2) compounds of formula I, in particular of formula

Ia, in which Rg represents a hydrogen atom,

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

4) Compounds in which R ₂ represents an alkyl group containing 1 to 3 carbon atoms, preferably a methyl group,

5) compounds in which it represents a phenyl group, optionally substituted with a R 6 group,

6) compounds in which R 8 is a hydrogen atom or a C 1 -C 3 alkyl group optionally substituted by one or more substituents selected from the group consisting of halogen, methoxy and methylthio;

7)

8) compounds wherein R 1 is a phenyl ring optionally substituted with R 2? and compounds of Formula I wherein W is O.

In the following, the invention will be further elucidated by means of specific examples thereof, and are not to be construed as limiting the scope of the invention as set forth in 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 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) of N, N'-carbonyldiimidazole, whereupon the mixture is allowed to react up to an eye of Wi

- 57 ««

the moment when 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 SiCl2, eluting with a 65:35 mixture of ethyl acetate and heptane. The product-containing fractions were then concentrated under reduced pressure to give 4.80 g (0.0154 mol) of 2-propionylamino-2-phenyl-2'-phenylpropionohydrazide.

Melting point: 144 ° C, yield: 61%.

The same procedure gives compounds 101 to 109 and 112 of the following table, which are intermediates for the preparation of compounds 1 to 9 and 12 - NH -

R

C-NH-NH-R ₄ µ!

O

C. R: R. Yield M.p. 101 Ph Me Ph 53% 150 [deg.] C 102 Ph Et Ph 61% 144 ° C 103 Ph cf ₃ Ph 50% 161 ° C 104 Ph CCIj Ph 49% 187 ° C 105 Ph nPr Ph 55% 102 ° C 106 Ph iPr Ph 45% 130 [deg.] C 107 Ph tBu Ph 77% 134 ° C 108 4-Cl-Ph Me Ph 71% 180 ° C 109 4-Cl-Ph Me 2-Me-Ph 64% 152’C 112 Ph ClCHj Ph 55% 146 ° C

Example 2

Preparation of the hydrazide 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 and 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 the 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 room temperature, washed with dilute sodium hydroxide solution and water, dried over magnesium sulfate, filtered and evaporated. 1.4 g (78% yield) of a white solid are thus obtained, having a melting point of 162 DEG C. and the formula:

OH ₀

Example 3

This example illustrates the preparation of compounds of Formula Ia by Method B by cyclizing compounds of Formula VII: Preparation of 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'-phenylpropionohydrazide and 0.17 g (0.001 mol) of paratoluenesulfonic acid in 25 ml of toluene is maintained at reflux temperature for 7 hours, forming the water is removed. The reaction mixture is then concentrated under reduced pressure and the residue is chromatographed on 200 g of SiC2, eluting with a mixture of ethyl acetate and heptane (50% / 50%). A thick oil is isolated which crystallizes after trituration in diisopropyl ether. 0.5 g (0.0018 mol) was isolated after filtration

2,4-Dimethyl-4-phenyl-1-phenylamino-2-imidazolin-5-one (Compound No. 1 (36% yield)) as a white powder melting 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.

C. Ri r ₃ R < Výy | ^ ek M.p. • - 1 Ph Me Ph 36 135 ° C 2 Ph Et Ph 86 copper 3 Ph CF, Ph 66 104 ° C 4 - Ph - CCl ₃ Ph - 14 68 ° C 5 Ph nPr Ph 84 copper 6 Ph iPr Ph 69 122 [deg.] C 7 Ph tBu Ph 11 87’C 8 4-Cl-Ph • Me Ph 54 140 [deg.] C 9 4-Cl-Ph 'Me 2-Me-Ph 65 142 [deg.] C 12 Ph C1CH ₂ Ph 79 77 ° C 14 Ph Et Ph 53 78 ° C 15 Dec Ph Et 2-Me-Ph 68 107 ° C 16 Ph Me 2-Mc-Ph 53 Mp 180 ° C 18 Ph MeOCH ₂ Ph 8 95’C 19 Dec Ph MeOCH ₂ 3-Cl-Ph 20 May 125’C 26 4-Mc-Ph Me Ph ' 41 142’C 29 Ph MeOCH ₂ 2-Me-Ph 54 122 [deg.] C 33 4-Me-Ph cf ₃ Ph 35 Mp 166 ° C 45 Ph MeOCH ₂ 2.3-diMe-Ph 55 91 ° C

Example 4

Preparation of the compound of formula Ia by method C11): preparation of 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-2-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 temperature of the reflux was maintained for one hour. Created by

da was removed by azeotropic distillation and the mixture was concentrated under reduced pressure. The crude product is then purified by silica gel chromatography. 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) was obtained in 18% yield. . _

Melting point: 164 ° C.

Example 5

Preparation of the compound of formula (Ia) according to method C12); Preparation of 2,4-dimethyl-4- (4-chlorophenyl) -1- (2-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 is refluxed 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 was then concentrated and the product 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 yielded compound 13 in a yield of 33.5%.

Compounds of formula (I) are also obtained in the same manner

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

C. r ₃ Yield(%) M.p. 13 4-Br-Ph Me Ph 34 147 ^e C 17 4-Cl-Ph Ph 3-Cl-Ph 31 120 [deg.] C 20 May Ph Me 3-Cl-Ph 43 163 ° C 21 4-Cl-Ph Et Ph 27 Mar: 144 ° C 22nd 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 May Mp 110 ° C '25 4-Cl-Ph Me iPr 53 copper 30 4-F-Ph Me Ph - 150 ^e C 31 PhCH ₂ Me Ph - Mp 192 ° C 32 PhCH ₃ . Et Ph - 167’C 34 Ph Me 4-iPr-Ph 20% 162’C 35 Ph Me 2,3-diMe-Ph 16% 64’C 36 Ph Me 2,3-diCl-Ph 33% 165’C 37 Ph Me 2,4-diMe-Ph 43% 100’C 38 Ph Me 3,4-diMe-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 [deg.] C 43 Ph Et 3-Cl-Ph 26% 82’C

C. R: r ₃ R < Yield(%) M.p. 44 Ph Et 2,3-diCl-Ph 41% 60 ° C 46 Ph Et 3,4-diMe-Ph 32% 94 ° C 47 Ph Et 2,3-diMe-Ph 27% 109 ° C 48 Ph Et 2,4-diMe-Ph 50% Deň: 32 ° C 49 Ph Et 4-Cl-Ph 48% 73 ^e 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-PhO-Ph Me Ph 54% 134’C 56 4-PhO-Ph Et Ph 58% copper 59 3-Cl-Ph Et Ph 49% 117 ° C

Similarly, spiro compounds 27 (yield 56%, melting point: 203 ° C) and 28 (yield 56%, melting point: 753 ° C) of the formulas were obtained:

Example 6

Preparation of compounds of formula Ia in which H is hydrogen and intermediates of formula VIII thereof by Method E.

a) To a solution of phenylhydrazine (2.25 g, 0.0208 mol) in diethyl ether (50 ml) was added methyl phenyl phenyl glycine chloride hydrochloride (4.58 g, 0.0208 mol) all at once 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 basified slowly 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 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) melting at 154 is isolated. Deň: 32 ° C. Yield: 38%.

In the same way, the phenylpropionohydrazides of the formula VIII h ₂ n (VIII) * 5 are obtained, the chemical structure, yield and melting point of which are given in the following table.

C. ^R i r ₂ r ₅ Výfjfek T.t. 155 Ph Me Ph H 38% 154 [deg.] C 157 Ph Me 2-Me-Ph H 32% 115 ° C 158 Ph Me 3-Cl-Ph H 20% 1664 ° C 160 Ph Me 2-Cl-Ph H 68% 112 ^e C 161 Ph Me 4-Cl-Ph H 48% 177 ° C 163 Ph Me 2-F-Ph H 43% 112 [deg.] C 164 Ph Me 4-F-Ph H 40% 142 [deg.] C 165 Ph Mc 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% 160 ° C

In a similar manner, spiro compound 162 (R 1 = C 8 H 4, R ₂ = (CH ₂ ) ₂ , R 1 = H, R 4 = Ph, 7% yield, melting point: 171 ° C) was obtained.

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

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

In the same way, compounds of formula (Ia) in which R @ 1 is hydrogen, i.e. compounds of formula R @ ₂ * 1 '

Their chemical structure, yield and melting point are shown in the following table.

C. Ri r ₂ ⁱⁿ W ^{e :} T. t. 54 4-F-Ph Me Ph 53% 140 [deg.] C 55 Ph Me Ph 38% 129 [deg.] 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 [deg.] C * 62 c ₈ h, (CH ₂ ) ₂ Ph 64% 202 DEG 63 Ph Me 2-F-Ph 86% 151 [deg.] 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 [deg.] 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 finely grinding, having the following composition:

- active substance: 60 mg

- Tween 80 surfactant (polyoxyethylenated sorbitan oleate) diluted to 10% with water: 0.3 ml

- adjust the volume to 60 ml with water.

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

Vine cuttings (Vitis vinifera), Chardonnay, 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.

Plants used as a 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 suspension of Plasmopara viticola spores, which suspension is obtained from a 4- to 5-day culture followed by suspension at a concentration of 100,000 units per cm.

The infected plants are then incubated for two days at about 18 ° C, in an atmosphere saturated with 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 is observed at a dose of 1 g / l for the following compounds:

1, 2, 3, 13, 15 to 18, 20 to 22, 24, 26 to 30, 35, 37 to 57, to 62, 64 to 67.

Example 8

In vivo test for Puccinia recondita

An aqueous suspension is prepared by finely grinding

a test drug having the following composition:

- active substance: 60 mg

- Tween 80 surfactant (polyoxyethylenated sorbitan oleate) diluted to 10% with water: 0.3 ml

- adjust the volume to 60 ml with water.

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

Wheat sown in small pots into a 50:50 peat / solid volcanic tuff substrate is treated at 10 cm by spraying with the above aqueous suspension.

After 24 hours, an aqueous spore suspension (100,000 spores / cm @ 2) was sprayed on wheat. This suspension is obtained from infected germinal plants. The wheat is then placed in an incubation chamber for about 24 hours at a temperature of about 20 ° C at 100% relative humidity and then for 7-14 days at 60% relative humidity.

Monitoring of seedlings is performed between the eighth and fifteenth days after infection by comparison with untreated control plants.

Under these conditions, good (at least 75%) or complete protection is observed at a dose of 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 fine grinding, an aqueous suspension of the active substance to be tested having the following composition is prepared:

- active substance: 60 mg

- Tween 80 surfactant (polyoxyethylenated sorbitan oleate) diluted to 10% with water: 0.3 ml

- adjust the volume 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 (5-6 leaf stage, plant height 12-15 cm), they are sprayed with an aqueous suspension having the above composition. Spray suspensions have different concentrations of the test drug.

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

After this infection, tomato seedlings are incubated for 7 days at about 20 ° C in a humidified atmosphere.

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, 24, 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 different classes, such as

Phycomycetes,

Basidiomycetes,

Ascomycetes,

Adelomycetes or fungi imperfecti,

 in particular against peronospora, grape rust and late blight.

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 may 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, penetration agents, stabilizers, complexing agents, and the like. More generally, the compounds used in the invention may 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% (by weight) 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,

silica, resin, 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 surfactants. For example, polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), sulfosuccinic acid ester salts, especially taurine derivatives (especially alkyltaurates) may be mentioned. , phosphoric acid esters of polyoxyethylenated alcohols or phenols, fatty acid esters of polyol, 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 therefore 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 is preferably 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, in particular granules obtained by extrusion, compression, impregnation of a granular carrier or powder granulation (the content of the compound in these granules being between 0.5 and 80%). for the latter cases), tablets and effervescent tablets.

The compounds of formula (I) may also be used in the form

A composition comprising 50 g of active ingredient and 950 g of talc may also 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, wettable powders (or sprayable powders), pastes or gels .

Emulsifiable or soluble concentrates most often contain 10 to 80% active ingredient, while emulsions or solutions ready for application 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 mentioned above.

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

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

Example EC 1

- the active substance '400 g / l

- alkali metal dodecylbenzenesulfonate 24 g / l

- oxyethylenated nonylphenol containing 16 g / l of ethylene oxide

- cyclohexanone 200 g / l

- make up the aromatic solvent to 1 l

According to another regulation for emulsifiable concentrate the following are used:

Example EC 2

- the active substance 250 g

- epoxidized vegetable oil 25 g

- mixture of alkylarylsulfonate and polyglycol ether and fatty alcohol 100 g

- dimethylformamide 50 g

- Xylene 575 g

Suspension concentrates, which can also be applied by spraying, are prepared to form a stable, non-settled 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; 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 now serves:

Example SC 1

- active substance 500 g - polyethoxylated tristyrylphenyl phosphate 50 g - polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (anti-foaming agent) i g - polysaccharide 1.5 g - water 316.5 g

Wettable 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 penetrating agents, adhesives, anti-caking agents, dyes, and the like.

To obtain sprayable or wettable powders, the active ingredients are intimately mixed in suitable mixers with the other ingredients and milled 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 produced instead of wettable powders. The conditions and methods for making and using these pastes are similar to those of wettable powders or powders

spray application.

As an example, the compositions of various wettable powders (or powders for spray application) are now given:

Example WP 1

- active substance 50% - ethoxylated fatty alcohol (wetting agent) 2.5% - ethoxylated phenylethylphenol (dispersant) 5% - chalk (inert carrier) 42.5%

Example WP 2

- active substance 10%

- C ₁₃ branched synthetic oxo alcohol

chain ethoxylated 8 to 10 mol ethylene oxide (wetting agent) 0, 75% - neutral calcium lignosulfonate (dispersant) 12% - calcium carbonate (inert filler) up to 100% Example WP 3

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

- active substance 75% - wetting agent 1.50% - dispersant 8%

- calcium carbonate (inert filler) supplement up to 100%

Example WP 4

- active substance 90%

- ethoxylated fatty alcohol (wetting agent) - - 4% - ethoxylated phenylethylphenol (dispersant) 6%

Example WP 5

- active substance 50%

- mixture of anionic and non-ionic surfactants (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 diluting a wettable powder or an emulsifiable concentrate of the invention with water. The emulsions may be of the water-in-oil or of the oil-in-water type and may have a thick consistency, such as mayonnaise.

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

These dispersible granules, with an apparent density generally lying between about 0.3 and 0.6, have a particle size generally between about 15 and 2000 _from µm, and preferably between 300 and 1500 _from µm.

The active ingredient content of these granules is generally between about 1% and 90%, and is preferably between about 25% and

The remainder of the granule is essentially comprised of a solid filler and optionally surfactant excipients which ensure the dispersibility of the granule in water. These granules may be essentially of 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, for example, kaolin or bentonite. The filler is preferably in combination with surfactants (in an amount of 2 to 20% by weight of the granule) 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 alkaline earth metal, and the remainder being nonionic or anionic surfactants 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.

Granule. according to the invention, it can be prepared by mixing the necessary ingredients and then granulating according to several methods known per se (granulator, fluidized bed, spraying, extrusion and the like). Generally, the preparation is terminated by crushing and subsequent sieving through sieves to the desired particle size in 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 of active ingredient 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 roller extruder. A granule is obtained which is dried, and then crushed and sieved, so as to keep only the granules having a size of between 150 and ₂₀₀₀ microns.

Example DG 2

Dispersible granules

The following ingredients are mixed in the mixer:

- active substance 75%

- wetting agent (sodium naphthalenesulfonate) 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 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 ingredients, in particular fungicides, which are in the form of wettable powders or granules or aqueous suspensions.

As regards the means which are suitable for:

TV 3 2 $ 7- Τ 'γ storage and transport, it is preferable to contain 0.5 to 95% by weight of the 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 plants or the place on which 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.

MB

Claims (27)

Compounds containing an imidazolinone or imidazolinethion group of the general formula I (I) in which W is S or O is n or 0, A is NR 8 or O or S or CR 4 R 8 or SO 2 or C = O, _R1 and R2, which are identical or different, represent a hydrogen atom, provided that one of the two groups being different from hydrogen, or an alkyl or haloalkyl group each containing 1 to β carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonylalkyl, monoalkylaminoalkyl, alkenyl or (C 2 -C 6) alkynyl or C 3 -C 7 dialkylaminoalkyl or cycloalkyl or aryl comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl , isoquinolyl or methylenedioxyphenyl 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 are as defined above, or R 1 and R 2 together with the carbon 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 or haloalkyl group containing from 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkylcarbonyl or alkoxyalkylalkyl, of 3 to 6 carbon atoms; or N, N-dialkylcarbamoylalkyl / a group containing 4 to 8 carbon atoms, R. represents 4 hydrogen when n is 1 or alkyl having 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl having 2 to 6 carbon atoms or dialkylaminoalkyl, alkoxycarbonylalkyl or an N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms; or N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazoles SUBSTI Τ - 46 ΉΕΕΤΤ, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl 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 - an alkyl group containing 1 to 6 carbon atoms, - an alkoxyalkyl, alkenyl or alkynyl group containing from 3 to 6 carbon atoms, - cycloalkyl having 3 to 7 carbon atoms, arylalkyl, phenyl or naphthyl optionally substituted as defined above 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, R1 represents a hydrogen atom when it is not a hydrogen atom or an alkyl, haloalkyl, alkylsulfonyl or halogenoalkylsulfonyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkyl containing 2 to 6 carbon atoms; or SUBS V- ·· - 1 alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl group having 3 to 6 carbon atoms or a formyl group or cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl group containing 3 to 6 carbon atoms atoms or phenyl, arylalkylcarbonyl, especially phenylacetyl and phenylpropionyl, arylcarbonyl, especially benzoyl, optionally substituted with 1 to 3 groups selected from R z, thienylcarbonyl, furylcarbonyl, pyridylcarbonyl, benzyloxycarbonyl, benzyloxycarbonyl, , tetrahydrofurfuryloxycarbonyl, thienylmethoxycarbonyl, pyridylmethoxycarbonyl, phenoxycarbonyl or (phenyl thio) carbonyl the phenyl group itself being optionally substituted by 1 to 3 groups selected from the meanings indicated for R 1, (alkylthio) carbonyl, (haloalkylthio) carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl group , (furfurylthio) carbonyl, (tetrahydrofurfurylthio) carbonyl, (thienylmethylthio) carbonyl, (pyridylmethylthio) carbonyl or arylsulfonyl or carbamoyl, optionally mono- or disubstituted an alkyl or haloalkyl group containing from 1 to 6 carbon atoms, or cycloalkyl, alkenyl or alkynyl having 3 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl or cyanoalkylSHEET - 48 j SUBST! l .. a (C 2 -C 6) carbon atom; - a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R 6, a sulfamoyl group optionally mono- or disubstituted an alkyl or haloalkyl group containing 1 to 6 carbon atoms, or cycloalkyl, alkenyl or alkynyl having 3 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl or cyanoalkyl of 2 to 6 carbon atoms - a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R 6, an alkylthioalkylsulfonyl group having 3 to 8 carbon atoms or a cycloalkylsulfonyl group having 3 to 7 carbon atoms, R. 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 given for R @ 2 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 halo-cycloalkyl group or an alkenyloxy, alkynyloxy, alkenylthio or alkenylthio group having 3 to 6 carbon atoms or a nitro or cyano or amino group, optionally a mono- or disubstituted alkyl or acyl group having 1 to 6 carbon atoms SUBSTIT SHEET - 49 carbon atoms or an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenyl group, a phenoxy group or a pyridyloxy group, these groups being optionally substituted, their salts and optically active isomers, with the proviso that: - when n = 0, then R ₄ is other than an optically active residue derived from an optically active primary amine or an optically active amino acid, - when n = 1, then AR ₄ is other than an optically active residue derived from an optically active primary amine or an optically active amino acid, - when n = 1 and A is SO ₂ , then one of the 2 groups or R ₂ is necessarily an aryl group, - when Ri and R ₂ simultaneously represent a phenyl group, and n is 1, and - when R and R ₂ simultaneously represent a p-methoxyphenyl group, n is at least 1. Compounds according to claim 1 of the general formula Ia W Know · ¹ '' ί? • ι.Κί ¹ '.' Ί · wherein R ₁ and W have the meanings given in claim 1. Compounds according to claim 1 or 2, wherein R 1 represents a hydrogen atom. Compounds according to any one of claims 1 to 3, wherein R 1 and R ₂ are other than hydrogen. Compounds according to any one of claims 1 to 4, wherein R ₂ represents an alkyl group having 1 to 3 carbon atoms. Compounds according to claim 5, wherein R ₂ represents a methyl group. Compounds according to any one of claims 1 to 6, wherein: R 1 represents a phenyl group, optionally substituted with R 6. / 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 1 represents a hydrogen atom. Compounds according to any one of claims 1 to 9, wherein R 1 represents a phenyl group optionally substituted by a group R ₇ . Compounds according to any one of claims 1 to 10, in which W represents an oxygen atom. 12. A fungicidal composition comprising, 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 formula I in which: W is S or O or S = O, n is 0 or 1, A is NR 8 or O or S or CR 4 R 8 or SO ₂ or C = O, R 1 and R ₂ , which are the same or different, represent a hydrogen atom, provided that one of the two groups is different from the hydrogen atom, or an alkyl or haloalkyl group containing 1 to 6 carbon atoms or alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl a group containing from 2 to 8 carbon atoms or a dialkylaminoalkyl or cycloalkyl group containing from 3 to 7 carbon atoms or an aryl group comprising a phenyl group, a naphthyl group, a thienyl group, a furyl group, a pyridyl group, a benzothienyl group methylenedioxyphenyl 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 ₁ and R ₂ together with the carbon 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 above for R ₇ , R ^ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkylcarbonyl, alkoxycarbonylalkyl or alkoxycarbonylalkyl up to 6 carbon atoms; or Ν, Ν-dialkylcarbamoylalkyl having 4 to 8 carbon atoms, R ^ represents a hydrogen atom when n is 1, or an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl having 3 to 6 carbon atoms; N, N-dialkylcarbamoylalkyl having 4 to 8 carbon atoms or an aryl group including phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl 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 - an alkyl group containing 1 to 6 carbon atoms, - an alkoxyalkyl, alkenyl or alkynyl group containing 3 to 6 carbon atoms, - cycloalkyl having 3 to 7 carbon atoms, arylalkyl, phenyl or naphthyl optionally substituted as defined above 1 to 3 groups selected from the meanings indicated for R 6 or - thienylmethyl or furfuryl, pyrrolidino, piperidino, morpholino or piperazino, optionally substituted with 1 to 3 carbon atoms, R 8 is a hydrogen atom when R 6 is not a hydrogen atom, or (C1 -C6) -alkyl, haloalkyl, alkylsulfonyl or haloalkylsulfonyl or alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl or alkoxyalkoxyalkoxyalkoxy to 6-alkoxy, (C 3 -C 6) or formyl or cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or (C 3 -C 6) alkynylcarbonyl or (C 4 -C 8) cycloalkylcarbonyl or phenyl, arylalkylcarbonyl, in particular phenylpropionyl and especially phenylacetylethyl; an arylcarbonyl group, especially a benzoyl group, optionally substituted by 1 to 3 groups m of the meanings given for R 6, thienylcarbonyl, furylcarbonyl, pyridylcarbonyl, benzyloxycarbonyl, furfuryloxycarbonyl, tetrahydrofurfuryloxycarbonyl, thienylmethoxycarbonyl, pyridylmethoxycarbonyl, optionally substituted phenyl, or phenoxycarbonyl; up to 3 groups selected from R ^, (alkylthio) carbonyl, (haloalkylthio) carbonyl, (alkoxyalkylthio) carbonyl, (cyanoalkylthio) carbonyl, (benzylthio) carbonyl, (furfurylthio) carbonyl, (tetrahydroiurfurylthio) a carbonyl group, a (thienylmethylthio) 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 cycloalkyl, alkenyl or alkynyl having 3 to 6 carbon atoms,. 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 indicated for R 6, 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, or - an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms, or - a phenyl group optionally substituted with 1 to 3 groups selected from the meanings indicated for R 6, an alkylthioalkylsulfonyl group having 3 to 8 carbon atoms or a cycloalkylsulfonyl group having 3 to 7 carbon atoms, R 8 represents a hydrogen atom or a cyano or C 1 -C 6 alkyl group or a C 3 -C 7 cycloalkyl group or a C 2 -C 6 acyl or alkoxycarbonyl group or a benzoyl group optionally substituted by 1 to 3 groups selected from the meanings listed for R- ,, R 6 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 halo-cycloalkyl group or an alkenyloxy-, alkynyloxy-, alkenylthio- or alkynylthio- group containing 3-6 carbon atoms or a cyano group or an amino group, optionally a mono- or disubstituted C 1 -C 6 alkyl or acyl group or a C 2 -C 6 alkoxycarbonyl group, a phenyl group, a phenoxy group or a pyridyloxy group, these groups are optionally substituted with their salts and the optically active isomers. Fungicidal composition according to claim 12, characterized in that it contains 0.05 to 95% by weight of the compounds according to any one 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. Process according to claim 14, characterized in that the effective amount is 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. 17. A process for the preparation of compounds of formula (Ia) characterized in that the compound of formula (VII) is prepared Ra - C - NH II o C-NH- _NR4 II (VII) r _{2 is} cyclized in a hot solvent by acid catalysis. 18. The process of claim 17 wherein 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 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 formula (Ia), characterized in that hydrazine of formula (I) is used R.NR NH _{C O} indicate hot reacted with Azalactone of vzor4 5 2 CE VI in an inert solvent in the presence of an acid catalization reaction. for the purpose of ka 22nd The method of claim 21 wherein the solvent is selected from the group consisting of aromatic solvents, halogenated hydrocarbons, esters and alcohols. 23. The process of claim 21 wherein the acid is selected from the group consisting of inorganic acids, alkylsulfonic acids, arylsulfonic acids, acidic resins, or carboxylic acids. The method according to claim 21, characterized in that it is carried out at a temperature of 50 to 150 ° C. 25. A process according to claim 21, wherein the hydrazine of the formula R &lt; 2 &gt; NR &lt; 6 &gt; 26. A process for the preparation of compounds of formula (Ia) in which R1 is hydrogen, characterized in that dimethylformamide dimethylacetal is reacted with an aminohydrazide of formula (VIII) according to the equation: The value of NK — N r ₅ * (ch ₃ ) ₂ nck (ock ₃ } ₂ R (VIII) R, ík Λ (Ia) Process according to Claim 26, characterized in that the γο H reaction is carried out at a temperature of 10 to 100 ° C, preferably in an excess of dimethylformamide dimethyl acetal.